Organometallic chemistry. : a review of the literature published during 1986

Organometal I ic Chemistry ~~

Volume 16

A Specialist Periodical Report

Organometallic Chemistry Volume 16 ~

A Review of the Literature Published during 1986

Senior Reporters E. W. Abel, Department of Chemistry, University of Exeter F. G . A. Stone, Department of lnorganic Chemistry, University of Bristol

Reporters D. A. Armitage, Kings College, University of London M. Bochmann, University of East Anglia B. J. Brisdon, University of Bath D. A. Edwards, University of Bath P. G . Harrison, University of Nottingham W. E. Lindsell, Heriot- Watt University D. R. Russell, University of Leicester A. K. Smith, University of Liverpool T. R. Spalding, University College, Cork J. L. Wardell, University of Aberdeen M. W. Whitley, University of Manchester J. W. Wilson, University of Ulster at Coleraine M. J. Winter, University of Sheffield A. H. Wright, University of Nottingham

SOCIETY OF CHEMISTRY

ISBN 0-85186-641-7 ISSN 0301 -0074

Copyright 0 1987 The Royal Society of Chemistry

All Rights Reserved No part of this book may be reproduced or transmitted in any form or by any means - graphic, electronic, including photocopying, recording, taping or information storage and retrieval systems - without written permission f iom the Royal Society of Chemistry

Published by The Royal Society of Chemistry Burlington House, London, W 1V OBN

Printed in Great Britain at the Alden Press, Oxford, London and Northampton

V

Foreword

This volume of the Specialist Periodical Reports "Organometallic Chemistry" surveys the literature for the calendar year 1 9 8 6 in a format similar to that used in previous volumes in the series. The continued growth of this area of chemistry, together with the need to limit these books to a reasonable length, and yet provide comprehensive coverage, necessitates presentation of the subject matter in a highly condensed manner. Nevertheless, we believe the book, like its predecessors, provides research workers with a valuable compendium of progress in the field.

E.W. A b e l

F . G . A . S t o n e

Contents

CHAPTER 1 Group I: The Alkali and Coinage Metals B y J. L. Werdell

1 A l k a l i Metals 1.1 G e n e r a l 1.2 H y d r o c a r b o n D i a n i o n Compounds

1.3 n-Complexes 1.4 A l k y l D e r i v a t i v e s

1.5 E n o l a t e s a n d R e l a t e d D e r i v a t i v e s

1.6 B e n z y l a n d R e l a t e d D e r i v a t i v e s 1.7 A r y l D e r i v a t i v e s 1.8 A l k e n y l a n d O t h e r U n s a t u r a t e d D e r i v a t i v e s

2 C o p p e r , S i l v e r a n d G o l d

2.1 n-Complexes 2.2 Y l i d e C o m p l e x e s 2.3 A l k y n y l a n d A l k e n y l D e r i v a t i v e s 2.4 A l k y l D e r i v a t i v e s 2.5 A r y l D e r i v a t i v e s

R e f e r e n c e s

B i b l i o g r a p h y

6 6 7 9 9 10

10

13

CEAPTER 2 Group 11: Alkaline Earths and Zinc and its Congeners By J . L. Wardell

1 B e r y l l i u m 14

2 Magnes ium 14

3 C a l c i u m a n d S t r o n t i u m

4 Z i n c a n d Cadmium

17

17

5 M e r c u r y 18

... Vlll Contents

5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8

General r-Complexes Methylmercury Complexes Other Alkyl Derivatives Aryl Derivatives Oxymercuration Alkynyl Compounds Miscellaneous Reactions

References

Bibliography

18 18 18 19 20 20 20 20

21

23

CHAPTER 3 Boron with the Exception of the Carbaboranes B y J.W. W i l s o n

1 Introduction 24

2 Books and Reviews 24

3 Uses of Organoboranes and Organoborates in Synthesis 24

4 Preparation and Reactions of Organoboron Compounds 28

5 Theoretical, Physical and Structural Studies on Organoboron Compounds 34

References 35

CHAPTER 4 Carbaboranes, including their Metal Complexes B y T.R. S p a l d i n g

1 Introduction, Review Articles and Theoretical Aspects 39

2 Carbaborane Synthesis, Characterisation and Reactions 40 2.1 C4-Carbaboranes 40 2.2 C2-Carbaboranes 40 2.3 C1-Carbaboranes 43 2.4 Physical Properties and Uses 43

3 a-Bonded Metallacarbaboranes 45

4 Cage Metallacarbaboranes 4.1 C4- and C3-Carbaboranyl Ligands 4.1 C2-Carbaboranyl Ligands 4.3 C1-Carbaboranyl Ligands

45 45 47 53

References 53

Contents ix

RlApTER 5

1

2

3

CHAPTER 6

1

2

3

4

5

6

7

8

9

10

11

G r o u p 111: A l U B l i n i ~ , GalliUm, IndiUm and -1liUm B y P.G. Harrison

R e v i e w A r t i c l e s 57

N o v e l Compounds, S t r u c t u r e s , S p e c t r o s c o p y a n d B o n d i n g 57

R e a c t i o n s a n d A p p l i c a t i o n s i n O r g a n i c S y n t h e s i s 73

R e f e r e n c e s 77

B i b l i o g r a p h y 80

G r o u p IV: The Silicon G r o u p B y D.A. Armitage

I n t r o d u c t i o n

The C a r b o n - M e t a l l o i d Bond

C a t e n a t i o n

H y d r o g e n D e r i v a t i v e s

R a d i c a l s a n d I o n i c D e r i v a t i v e s

N i t r o g e n Compounds

P h o s p h o r u s , A r s e n i c a n d A n t i m o n y D e r i v a t i v e s

Oxygen D e r i v a t i v e s

S u l p h u r , S e l e n i u m a n d T e l l u r i u m D e r i v a t i v e s

H a l o g e n D e r i v a t i v e s

C o m p l e x e s

R e f e r e n c e s

CHAPTER 7 G r o u p V: Arsenlc, Antimony and Bismuth B y J. L. Wardell

1 T e r v a l e n t Compounds

2 Q u i n q u e v a l e n t Compounds

3 Uses i n O r g a n i c S y n t h e s i s

4 B i b l i o g r a p h y

R e f e r e n c e s

84

85

98

100

102

104

108

110

116

117

118

119

142

143

144

144

145

X Contents

CHAPTgR 8 Metal Carbonyls By B . J . B r i s d o n

1 Introduction

2 General and Theoretical Studies

3 Chemistry of Metal Carbonyls 3.1 Mononuclear Carbonyl Derivatives 3.2 Binuclear Carbonyl Derivatives 3.3 Polynuclear Carbonyl Derivatives

4 Cluster Carbonyls containing C, N, P, As, S, Se or

5 Metal Carbonyl Hydrides

6 Metal Carbonyl Halides

References

147

147

149 149 150 151

Te152

153

154

155

CHAP= 9 Organometallic Compounds Containing Metal - Metal Bonds By W.E. L i n d s e l l

1 Introduction 1.1 Reviews 1.2 Theoretical Studies 1.3 Physical Studies 1.4 Surface Bound Species

160 160 160 161 161

2 Compounds with Homonuclear Transition Metal Bonds 162 2.1 Titanium 162 2.2 Vanadium 162 2.3 Chromium, Molybdenum and Tungsten 162 2.4 Manganese and Rhenium 165 2.5 Iron 166 2.6 Ruthenium and Osmium 168 2.7 Cobalt 172 2.8 Rhodium and Iridium 173 2.9 Nickel 175 2.10 Palladium and Platinum 176 2.11 Copper and Gold 176

3 Compounds with Heteronuclear Transition Metal Bonds 177 3.1 Binuclear Complexes 177 3.2 Tri- and Higher Nuclearity Complexes 180

Contents xi

4 Compounds c o n t a i n i n g B o n d s b e t w e e n T r a n s i t i o n a n d Main G r o u p Metals 185

4.1 L i t h i u m 185 4.2 Magnesium 185 4.3 M e r c u r y 185 4.4 G a l l i u m a n d T h a l l i u m 186 4.5 G r o u p I V 186 4.6 B i s m u t h 187


CHAPTER 10

1

2

3

4

5

6

7

8

Ligand Substitution Reactions of Metal and Organaneta1

By D.A. Edwards

R e v i e w s 201

Carbonyls with Group V and VI Donor Ligands

P a p e r s of G e n e r a l I n t e r e s t 20 1 2.1 N i t r o g e n Donor L i g a n d s 202

L i g a n d s 20 2 2.2 P h o s p h o r u s a n d t h e H e a v i e r Group V Donor

2.3 G r o u p V I Donor L i g a n d s 206

G r o u p s I V a n d V 206

G r o u p V I 207 4.1 C a r b o n y l C o m p l e x e s of C r o p Moo a n d Wo 207 4.2 C a r b o n y l C o m p l e x e s of Mo" a n d W1' 211 4.3 C y c l o p e n t a d i e n y l , A r e n e a n d O t h e r C o m p l e x e s 212

G r o u p V I I 213 5.1 C a r b o n y l , C a r b o n y l H a l i d e a n d R e l a t e d C o m p l e x e s 213 5.2 C y c l o p e n t a d i e n y l a n d A r e n e C o m p l e x e s 214

G r o u p VIII: I r o n , R u t h e n i u m a n d Osmium 215 6.1 I r o n , R u t h e n i u m , a n d Osmium C a r b o n y l C o m p l e x e s 215 6.2 C y c l o p e n t a d i e n y l C o m p l e x e s 218

Group VIII: C o b a l t , Rhodium a n d I r i d i u m 2 19 7.1 C a r b o n y l C o m p l e x e s 219 7.2 C y c l o p e n t a d i e n y l C o m p l e x e s 221

G r o u p VIII: N i c k e l , P a l l a d i u m a n d P l a t i n u m 222


xii Con tenrs

CBAPTER 1 1 Complexes Containing Metal - Carbon a-Bonds of the Groups Scandium to Manganese, Including Carbenes and Carbynes

B y Mark J. W i n t e r

1 I n t r o d u c t i o n 230

2 G r o u p 3 ( S c , Y, a n d L a ) , L a n t h a n i d e s a n d A c t i n i d e s 230

3 G r o u p 4 ( T i , Z r , a n d H f ) 231

4 G r o u p 5 ( V , Nb, a n d T a ) 237

5 G r o u p 6 ( C r , Mo, a n d W) 238

6 G r o u p 7 (Mn, T c , a n d Re)

R e f e r e n c e s

251

257

CBAPTER 12 Complexes Containing Metal - Carbon u-Bonds of the Groups Iron, Cobalt and Nickel

By A . R . S m i t h

1 I n t r o d u c t i o n , R e v i e w s a n d Ar t i c l e s o f G e n e r a l I n t e r e s t 265

2 Metal - C a r b o n a -Bonds i n v o l v i n g G r o u p VIII Metals 265 2.1 T h e I r o n T r i a d 265 2.2 T h e C o b a l t T r i a d 272 2.3 T h e N i c k e l T r i a d 277

3 C a r b e n e ' a n d C a r b y n e C o m p l e x e s o f t h e G r o u p VIII Metals 285

3.1 T h e I r o n T r i a d 285 3.2 T h e C o b a l t T r i a d 289 3.3 T h e N i c k e l T r i a d 29 1

B i b l i o g r a p h y 29 2


CHAPTER 13 Metal - Hydrocarbon r-Complexes, Other than r-Cyclopentadienyl and r-Arene Complexes

By M. W. W h i t l e y

A R e v i e w s

B A l l y 1 C o m p l e x e s a n d C o m p l e x e s D e r i v e d f r o m M o n o a l k e n e s

1 C r , Mo a n d W 2 F e , Ru a n d 0 s

302

302 302 303

Contents xiii

3 Co, Rh and Ir 4 Ni, Pd and Pt 5 Other Metals and Theoretical Studiea

C Complexes Derived from Unconjugated Dienes 1 Fe, Ru and 0s 2 Co, Rh and Ir 3 Ni, Pd and Pt 4 Other Metals

D Complexes Derived from Conjugated Dienes 1 Cr, Mo and W 2 Mn and Re 3 Fe, Ru and 0 s

(a) Acyclic Dienes (b) Cyclic Dienes

4 Co, Rh and Ir 5 Other Metals

E Complexes Derived from Acetylenes

F Polynuclear Complexes 1 Binuclear Complexes 2 Polymetallic Complexes

References

CHAPTER 14 r-Cyclopentadienyl, r-Arene and Related Complexes B y A . H . W r i g h t

1 Introduction

2 Monocyclopentadienyl Complexes 2.1 Titanium, Zirconium and Hafnium 2.2 Vanadium, Niobium and Tantalum 2.3 Chromium, Molybdenum and Tungsten 2.4 Manganese and Rhenium 2.5 Iron, Ruthenium and Osmium 2.6 Cobalt, Rhodium and Iridium 2.7 Nickel, Palladium and Platinum 2.8 Lanthanides and Actinides

3 Biscyclopentadienyl Complexes 3.1 Titanium, Zirconium and Hafnium 3.2 Vanadium, Niobium and Tantalum 3.3 Chromium, Molybdenum and Tungsten

305 307 308

310 3 J$ 310 310 31 1

311 31 1 314 314 314 316 318 319

32 1

323 323 330

340

351

352 352 352 354 355 357 358 361 36 1

361 36 1 364 364

XiV Contents

3.4 Manganese and Rhenium 3.5 Iron, Ruthenium and Osmium 3.6 Cobalt and Nickel 3.7 Scandium, Lutetium, Lanthanides and Actinides

4 Tricyclopentadienyl Complexes

5 Arene Complexes 5.1 Vanadium, Niobium, Tantalum and Zirconium 5.2 Chromium, Molybdenum and Tungsten

Bisarene Complexes 5 .3 Manganese and Rhenium 5 .4 Iron, Ruthenium and Osmium 5 .5 Other Arene Complexes

References

CHAPTER 15 Eomogeneous Catalysis by Transition Metal Complexes By M . Bochmann

1 General

2 Hydrogenation and Reductions

3 Asymmetric Hydrogenations

4 Hydrogen Transfer Reactions

5 Isomerisations and Rearrangements

6 Hydrosilylations

7 Addition Reactions to C=C and CEC Bonds

8 Alkene Dimerisations and Oligomerisations

9 Alkyne Oligomerisations

10 Alkene Polymerisations

11 Alkene Metathesis

12 Alkyne Polymerisations

13 Carbonylations 13.1 Carbon Monoxide Reductions 13.2 Water Gas Shift 13.3 Carbonylations and Homologations of Alcohols

13.4 Hydroformylations 13.5 Carbonylations of Organic Halides

and Esters

365 365 367 367

368

369 369 369

371 37 1 37 3 375

376

385

387

391

393

394

394

396

39 8

400

402

402

406

407 407 408

408 410 413

Con tents xv

15 Oxidations

References

417

418

CHAPTER 16 Structures of Organometallic Compounds determined by

By D. R. Russel 1 Diffraction Methods

1 Introduction 427

2 Main Table 428

3 Metals Cross Reference Table 487

References 489

Corrections to Metals Cross Reference Table in Chapter 16 of Volume 15 524

xvii

Abbreviations

Ac acac acacen Ad AIBN Ar ar phos ATP Azb 9-BBN biPY BZ Bzac cbd

chd chpt

1,5,9-~dt

[COI (CO) cod cot

CP CY dab dba DBU DCA depe depm diars diarsop

dien diop

diphos dipyam DME DMF dmg dmgH2 dmpe dmpm DMSO dpae dpam dPPa dPPb dPPe dPPm dPPP edt en

acetate (MeCoo-) acetylacetonate NN'-ethylenebis(acety1acetone iminate) adamant y l azoisobutyronitrile Aryl l-(diphenylphosphinio)-2-(diphenylarsino)ethane adenosine triphosphate azobenzene 9-borabicyclo[3.3.1]nonane 2,2'-bipyridyl benzyl benzoylacetonate cyclobutadiene cyclododeca-1,5,9-triene cyclohexadiene cycloheptatriene cobalamin cobaloxime [C~(dmg)~ derivative] cyclo-octa-1,5-diene cyclo-octatriene q5-cyclopentadienyl cyclohexyl 1,4-diazabutadiene dibenzylideneacetone 1,8-diazabicyclo[5.4.O]undec-7-ene 9,lO-dicyanoanthracene 1,2-bis(diethylphosphino)ethane 1,2-bis(diethylphosphino)methane o-phenylenebis(dimethy1)arsine {[2,2-dimethyl-1,3-dioxolan-4,5-diyl)bis-

(methylene)]bis[diphenylarsine]) diethylenetriamine ~[2,2-dimethyl-1,3-dioxolan-4,5-diyl)bis-

(methylene)]bis[diphenylphosphine]~ 1,2-bis(diphenylphosphino)ethane di-(2-pyridyl)amine dimethoxyethane NN-dimethylformamide dimethylglyoximate dimethylglyoxime 1,2-bis(dimethylphosphino)ethane bis(dimethy1phosphino)methane dimethyl sulphoxide 1,2-bis(diphenylarsino)ethane bis(dipheny1arsino)methane 1,2-bis(diphenylphosphino)ethyne 1,4-bis(diphenylphosphino)butane 1,2-bis(diphenylphosphino)ethane bis(dipheny1phosphino)methane 1,3-bis(diphenylphosphino)propane ethane-1,2-dithiolate ethylene-1,2-diamine

xviii Abbreviations

EXAFS Fgacac Fc

FVP

GVB hf a hf acac hfb HMPA LDA LiDBB Me6[14]dieneN4

FP

glyme

Me6 [ 14 IN4

4,7-Me2phen 3,4,7,8-Meqphen Me s mcpba na P nbd NBS NCS Pc PMDT Pd phen pmedta [ PPN]' PY PZ RDF sal salen saloph SCF TCNE TCNQ ter PY tetraphos

TFA tf acac tfo THF tht TMBD TMED (tmen) TMS to1 TP P triphos Tsi vi

extended X-ray absorption fine structure hexafluoroacetylacetonate ferrocenyl

flash vacuum pyrolysis ethyleneglycol dimethyl ether generalized valence bond hexafluoroacetone hexafluoroacetylacetonato hexafluorobutyne hexamethyl phosphoric triamide lithium diisopropylamide lithium di-t-butylbiphenyl 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetra-aza-

cyclotetra-4,ll-diene 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetra-aza-

cyclotetradecane 4,7-dimethyl-l,lO-phenanthroline 3,4,7,8-tetramethyl-l,lO-phenanthroline mesit y 1 metachloroperbenzoic acid 1-naphthyl norbornadiene N-bromosuccinimide N-chlorosuccinimide phthalocyanin p e n t a r n e t h y l e n e d i e t h y l e n e t e t r a m i n e pentane-2,4-dionate 1,lO-phenanthroline pentamethyldiethylenetriamine

pyridine pyrazolyl radial distribution function salicylaldehyde NN'-bis(salicyla1dehydo)ethylenediamine NN-bisalicylidene-o-phenylenediamine self consistent field tetracyanoethylene 7,7,8,8-tetracyanoquinodimethane 2 , 2 ' ,2"-terpyridyl 1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphospha-

trifluoroacetic acid trifluoroacetylacetonato triflate, trifluoromethylsulphonate tetrahydrofuran tetrahydrothiophen NNN'N'-tetramethyl-2-butene-l,4-diamine tetramethylethylenediamine tetramethylsilane

meso-tetraphenylporphyrin l,l,l-tris(diphenylphosphinornethy1)ethane tris(trimethylsily1)methyl (Me3Si)3C vinyl

Fe (CO) 2CP

[ ( P ~ ~ P ) ~ N I +

decane

tolyl

7 A

Group I: The Alkali and Coinage Metals

BY JTL. WARDELL

1 Alkali Metals

1.1 General. U1 trasoniu acceleration of the formation of organolithiums using metall ic lithium has been fur ther i l l u s t r a t e d ; ' c-LiCH2C6H4CH2Br, A n t h 2 - , 2 L i t , L i p cyclo-octatetraenide and L i z acenaphthenide were among the compounds prepared by t h i s route.

1.2 Hydrocarbon dianion compounds. Enthalpies of formation of ArH2-,2Nat (ArH= Naph, A n t h , tetracene, pentacene, pyrene, perylene, *.) from ArH and Na were calculated to be similar (g. 40 k cal mol"). e f fec ts rather than electron a f f i n i t i e s account f o r the d i f f icu l ty i n forming dianions of the smaller hydrocarbons.2 N . m . r . spectra have been obtained i n MF f o r K2 acepentalenide (from the hydrocarbon and BuLi,PetOK), Na2 bifluoran- 9-ylide (from metal reduction of the crowded alkene) and L i p biphenylide (from L i reduction of the hydrocarbon).

This suggests t h a t entropy

1.3 T-Complexes. provides4 ternary complexes w i t h both C2H4 and N2 co-ordinated to L i . deposition . of L i atoms and CO i n krypton matrices a t 12 K has been reported to produce5 various products, including Li(CO), [0=1,2,3,>4] and L i (CO) - n m - m = l or 2 ) ; SCF and post-SCF-CI calculations have a l so been carried out. these complexes, s ign i f icant electron transfer to the oxygen occurs, leading to large dipole moments f o r L i - C O and L i - C O - L i .

Co-condensation of L i atoms w i t h C2H4 and N2 i n so l id argon Co-

(n=2 or 3,

In

1.4 Alkyl derivatives. Mass peaks corresponding t o [Rn- lLin]+ (1) and the l e s s s tab le [HRn-2LiL]t have been observed i n the mass spectra OF (RLi) (2) between 10-70 eV. The ions, ( 1 , _?=4 o r 6) a re formed through a single step fragmentation o f [R L i It ( ~ = 4 o r 6) and these create a l l the remaining ions i n the m.s. by d i r e c t and consecutive fragmentations.6 In the gas phase, i t appears t h a t f o r (2, R=Me, Pri, Bus o r But) tetramers a re present while f o r (2, R=Pr, Bu o r Bu' ) , t e tramers and hexamers occur.

determined: L i - C (E. 2.E and 2.27 8) bond lengths; ( i i ) [( PMDT) L i ( u- C1) L i ( PMDT) [ L i {C( Si Me3) l2 } ] ( 4 ) ob t a i ned * from PMDT, L i C1 and

!l

n n

The crystal structures of the following u-silylmethyl-li thiums have been (i) [LiCH2SiMeg16 (3) {two sets of L i - L i ( a ~ . 2.48 and 3.18 8) and

L i . . . . H (methylene) z. 2.0 to 2.3 R>,'

[For references see page 10 1

2 Organometallic Chemistry

[Li(THF)4][LiCC(SiMe3)312] (5) [ i n (4), c a t i o n k s a l i n e a r LiCLi un i t ; essent ia l l y the same as t h a t i n (5 ) J and ( i i i ) [LiC(SiMe20Me)3]2 { long Li-C and shor t C - S i bonds; one OMe group o f C(SiMepOMe)3 i n each monomer u n i t co- ordinates to the L i i n the same monomer and the other two to the other L i i n the dimer.1'

The s t ructures o f o ther organoli thiums conta in ing in -bu i l t donor groups have been reported; (7)." chelat ing CH2CH2X (X=O& O r NMe2) groups. (methylene) are 2.12 to 2.16 8 i n (6) . spectra o f (6) ind ica te the s o l i d s ta te te t ramer is inequi l ibr ium w i t h a stereo- isomer. l i th iums i n PhH have been investigated;12 included i n t h i s study,were (6), (MeOCH2CH2CHMeLi)4, 2-Li -7-MeO-norbornane and MeO( CH2)5Li. Klumpp' has reviewed the oxygen o r n i t rogen ass is ted 1 i t h i a t i o n s and carbol i t h i a t i o n s o f non- aromatics. (ArH=PhPh o r Naph; derivatives, R'CH(0M)CHRM (9. R'=Ph o r R2C02, R1=H; R2=H, R1=alkyl). syntheses o f (LiCH2)3cyclohexane der iva t ives (8) have been a ~ h i e v e d ' ~ by cleavage o f PhS-C bonds i n appropriate compounds by [ButC6H4CsH4Butl-',Lit.

The c rys ta l s t ruc tu re and 1 3 C n.m.r. spectrum o f monomeric (Ph2P)2CHLi. TMED have been reported;16 I n the s o l i d s ta te s t ruc tu re o f { [LiCH2PPh2CH2]2(dioxane)312 (dioxane), the cent- r a l features" are two 8-membered r ings, i n the crown conformation; i s made up o f two (CH2PPh2CH2) l igands br idg ing two L i atoms. are l i n k e d (v& L i ) by a b r idg ing dioxane. acceptor groups on the s t a b i l i z a t i o n o f a ser ies o f H3P=CHX, inc lud ing X=Li, was studied by an ab i n i t i o M.O. method."

meta l la t ion o f RH by ByLi.TMED. (R'=R2=H)],.2TMED revealed a tetramer having two pa i rs o f d i f f e r e n t l y coordinated L i atoms and sulphoximide anions; one L i type i s co-ordinated t o 2 0

( L i - O c 1.90(5)/?) and t o 2 N ( L i - N E 2.10(5) R), whi le the other L i ' s are each bonded t o 3 N ( o f sulphoximide units') (Li-N 2.49(5) 8) w i t h add i t iona l contacts L i . . .L i (E 2.78(5) t ) and Li. . .C (other CH2) (E. 3.24(4) 8 ) . The S-C(H ) bond length ind icates s i g n i f i c a n t double bond character. con f igura t iona l l y s tab le i n THF so lu t ion a t the anion ic %. atom, even a t low temperature.

anion i s

namely ( LiCH2CH2CH20Me)4 (6 ) lo and (LiCH2CH2CH2NMe2)4 I n the c r y s t a l , both (6) and (7) have d i s t o r t e d (CH2)4Li4 cubes w i t h

Contacts between L i and H I n hydrocarbon solut ion, the n.m.r.

Enthalpies o f in t ramolecular co-ordination o f various methoxyal k y l -

Treatment14 o f epoxides, R'CHCHR 0, w i t h ArH-,M+ ( 2 equiv.) M=LiK o r $Mg) i n THF a t G. -80°C provides 6-alkoxyethyl

The

L i i s co-ordinated to bothPatoms (L i -P 2.58(2) 8 ) .

each r i n g The two r ings

The e f f e c t o f a-donor and T-

L i t h i o a l kylsulphoximides, MeN=S(0)PhCR1R2Li (9, R=Li), are obtained on The c rys ta l s t ruc tu re analys is o f [(S)-9

2.09(5) 8) and 2 C (CH2)(Li-C

2 1 2 I t was ca lcu lated from n.m.r. data t h a t (9, R f R ) are no t

,"- Pl Group I: The Alkali and Coinage Metals

C

3

(8 I (121 W

Organometallic Chemistry

1.5 Enolatesand re la ted derivatives. The lithium enolate of CH3CH0 (CH2=CHOLi ) i s z o tetrameric i n THF w i t h a bar r ie r to rotation about the vinyl bond of 6.6 kJ ml". The s t ruc tures of pinacolone enolates [H2C=CButOMln(THF)m ( M = L i , ~=m=4; M=Li , n=6, m=O; M=Na, 5=4, m=O; m=K, g=m=6) have been investigated." The solid s t a t e s t ruc tures (as well as those in solution) have been determined for the dimeric species ( i ) 1 i th ia ted 2-Me02-cyclohexanone dimethylhydrazone [as the THF so1vate;22 ( l o ) ] , ( i i ) l i t h i a t e d cyclohexanone phenyliminez2 [as the Pr12NH solvate; ( l l ) ] and ( i i i ) l i t h i a t e d pinacolone phenylimine as the Et20 ~ o l v a t e , ' ~ [CH2C=CButNPhLi)]2(Et20)2, (12) . occurs i n hydrocarbon solutions; mixture o f isomers i n solution. The structures have been discussed i n the l i g h t of the s e l e c t i v i t y of alkylations and a l so of the syn e f f e c t of l i t h i a t e d imi nes .

- -

Some dissociation o f (10) (11) e x i s t s as a rapidly equi l ibr ia t ing

1.6 Benzyl and related derivatives. - o-OMe; M = L i , Na, K o r C s ) i n THF has been investigated using conductometric techniques;'" metallating combination," BuLi-ButOK, has been used to obtain KOC6H4CH2K from cresols, and the tetraanionic species 3,5-(MCH2)2C6H4C6H4(CH2M)2-3,5 (13, M = K ) , from (13, M = H ) . In the d i l i t h i o species (14), prepared by L i reduction of the hydrocarbon (15), equation 1 , n.m.r. data i n ethereal solvents c lear ly indicate two d i f fe ren t Li atoms 6 0.61 and -1.09 ppm) and two d i s t i n c t carbanionic centres; for (14-6Li) 6 C6 59 ppm ( t , JC-Li 6.9 Hz (12. bonding to 1Li) and 6 C8 100 ppm

Dissociation of XC6H4CH2M ( X = H , p O M e o r

K d , AHd and ASd values have been obtained. The powerful

(*.no L i - C coup1 ing) .26 I t was argued tha t the structureis&fected by intramolecular interaction between the carbanion moiety and the remote .rr-system as well asby the interactions of the two carbanionic uni t s . 2,Z-Me2-cyclopropane and 8-M-8-Ph-2,3-benzo[3.2.l]octane RM ( M = L i , Na or K) (obtained from R - O k and M ) have been compared to those of (14) and the sodio analogue o f (1 4).

s t a t e structure of 2,6-(Me3SiCHLi)2-pyridine.2TMED i n agreement w i t h a MNDO

The n.m.r. spectra of Li-2-Ph-

Double ~3-aza-a l ly l - l i th ium interactions have been found" i n the so l id

Group I: The Alkali and Coinage Metals 5

ca lcu la t ion on the der ivat ive, 2,6-(H3Si CHLi )z-pyr id ine .4THF. have a lso been determined f o r ( i ) [PhS(0)CPhMeLi.TMEDJ2 (16) (a dimer w i t h a L i202 r i n g ) 2 a a and ( i i ) (PhCHLiCN.TMED)2.PhH (a dimer2eb w i th a Li2N2 r i n g and almost l i n e a r C-C-N). Only one diasteromer o f (16) was found i n the c rys ta l ; protonation o f (16) i n EtEO provides only (RR)/(SS)-PhCHMeSOPh. I t has been establ ished t h a t reac t ion of PhCHzR [R=CN o r P(0)(OEt)21 w i t h BuLi ( 2 equiv.) i n THF produces PhCHLiR.LiBu (17) ra ther than PhCLi2R. Der iva t isa t ion o f (17) can however provide d isubs t i tu ted products via a sequence invo lv ing meta l la t ion and a l k ~ l a t i o n . ~ ’ 9-R-1 OLi-9,lO-di hydroanthraoenes have a t t rac ted f u r t h e r a t ten t ion . 30

i n ~ e s t i g a t e d . ~ ’ f l ~ o r e n e . ~ ~ f o r a ser ies o f f l u o r e n e d e r h a t i v e s which form solvent separation ion-pai rs i n THF; ASo values were found to be small f o r the i n d i c a t o r e q u i l i b r i a , s tud ied by u .v. -v is spectroscopy.

Crystal s t ructures

The formation and stereochemistry o f a lky la t ions o f

Solvent e f f e c t s on the I 3 C n.m.r. spectra o f indeny l - l i th ium have been The pyro lys is o f 9-Li-fluorene a t 180°C provides 9,9-Li2-

An equ i l ib r ium l i t h i u m ion-pa i r i n d i c a t o r scale has been establ ished

1.7 Aryl der ivat ives. Enthalpies o f so lva t ion o f 2-ROC6H4Li and 8-Li-1-MeO- naphthalene i n Bu20 are lower than those o f the 4 - l i t h i o isomers3“ by z. 20 and 28 kJ mol” respect ive ly .

s o l u t i o n (as found using 6 Li-’H 2D heteronuclear Overhauser NMR spectroscopy) and i n the s o l i d s t a t e [from a c rys ta l s t ruc tu re determination o f (18. L i ... Hll 2 2.9 8 w i t h the next shor tes t L i .... H3 2 3.2 81. i n t e r e s t 3 5 t h a t f u r t h e r meta l la t ion of (18) occurs a t Cll.

are r a p i d l y o r t h o - l i th ia ted; d i r e c t i n g groups than i s MeO. to F, i n con t ras t to the s i t u a t i o n f o r uncomplexed FC6H40Me.

compound [L i .TMEDI2[1 ,2-C4H4(BNMe2)21 has been reported.” It can be considered as a contact i o n t r i p l e w i t h [Li.TMEDl above and below the planar C4B2 r ing . (Li-C 2.263(8) t o 2.368(7) 8; Li-B 2.471(8) to 2.553(8) 8 ) .

The c loses t Li. . .H contacts i n 2-Li-1-Ph-pyrrole (18) involves Hll i n both

I t i s o f

Rig id 2-Ph-1,3-dioxanes, having the aceta l proton i n an ax ia l o r i e n t a t i o n ,36 such r i g i d 1,3-dioxanyl groups are stronger ortho-

L i t h i a t i o n 3 ’ o f (FC6H40k)Cr(CO)3 occurs or tho

The synthesis and c r y s t a l s t ruc tu re o f the l i t h i u m 1,2-diboratobenzene

1.8 Alkenyl and other unsaturated der ivat ives. ‘Li i n THF revealed 1 dimeric and 3 d i f f e r e n t tetrameric aggregates; the tetramers probably on ly d i f f e r i n number o f THF molecules o f so lvat ion.39

cyclo-octene (s tab le a t 40°C b u t w i t h tt.1 h a t RT) and 2,2-Li2-1,l’-bicyclo- octenyl . I n contrast, 3-octyne slowly provided the trans-adduct.

A 1 3 C n.rn.r. study o f ButCz13C-

Cyclo-octyne reacts”Oa w i t h L i powder a t -35°C i n Et20 t o g ive c i s - 1 ,2-Liz-

The mechan-


ism for the isomerisation of trans-1 ,2-Li2-a1 kenes has been investigated using an ab-initio method.40b Configurational instabi l i ty was also reported ( i ) for (Z)-PhCLi=CHSiEt3 [obtained from BuLi and (L)-PhC(SnBu3)=CHSiEt3 a t -78°C ],'la ( i i ) (z)-Me3SiCM=CHR (19) [obtained"lb from (E)-Me3SiCI=CHR and ButLi ( 2 equiv)

1 2 in pentane/ether a t -78OC1, ( i i i ) R R C=CLiS02Ph, a t -60"C41c and41d (z)- EtSCH=CLiS(O)Et a t -80°C (both from MeLi and the appropriate alkene). most plausible isomerisation-mechanism for (19) involves a sywergistic or 'push-pull' interaction of the Li-C u bond and an empty orbital o i S i ; the rates o f isomerism, investigated by n.m.r. , depend on the electropositivity of M and on R ( for M = L i , R=p-XC6H4, p=-O.<l in Et20-pentane solution a t -20°C). (c) or (Z)-y-Alkoxyvinyl-metallic compounds, R 2 C ( O M ' ) C H = C H M (M=Li, M'=MgX; M'=MgX, M'=Li) have been synthesied,'+* from Me02CCH=CHC1 on successive treatment with RMgX ( 2 equiv) and Li powder. (20) has been produ~ed'~ from ButCXCHMeCXBut, BuNa and TMED in hexane; solid, Na co-ordinates t o the two chelating TMED units and a terminal carbon of the allene unit [Na-C3 2.595(9), Na ... C4 2.803(8) and Na ... C5 3.45(2) R l .

Bicyclo[3.2.1] octa-2,6-dienyl-lithium ( 2 1 ) has been isolated as the TMED adduct. A crystal structure determination of (21. TMED) indicated that Li i s bound to the carbanion by both a l ly l i c and olefinic bonding. As TMED i s also co-ordinated to Li , L i i s 7 co-ordinated; overall agreement44b with the X-ray structure of (21 .TMED). 13C N.m.r. spectra of ( 2 1 ) and various phenyl derivatives44c as well as K analogues have also been reported and discussed i n terms of the bishomoaromatic character of the anion.

Rates of i s o r n e r i s a t i ~ n ~ ~ of trans-neopentylallyl-M in THF increases in the sequence Li > Na > K . diglymeI2, from PhS02CH2CH=CH2 and BuLi i n diglyme, have been i n ~ e s t i g a t e d . " ~ I n the crystal , there i s a L i 202S2 ring w i t h a penta-co-ordi nate L i ( t o 5 0 ) ; the ally1 group l i e s outside the co-ordination sphere of Li. A homonuclear, 6 L i , 6Li s h i f t correlation experiment has been performed on Me2C=CLiCLi.-CMe2 in THF a t -70°C; two non-equivalent sets of Li were indicated in agreement with the sol i d s t a t e structure (of the te tramer ) . '+

out on C3H3Li. s table.48

The

or

t The compound [(TMED)2NaCBu =C=CMeCXBut] in the

the MNW structure of (21) shows

The crystal and solution structures of [PhS02CHLiCH=CH2.

An a b i n i t i o MO calculation a t electron correlated levels has been carried A singlet cyclic structure ( Cs) was calculated as the most

2 Copper, Silver and Gold

2.1 .rr-Complexes. Calculations, involving electron correlation effects, have been carried out on the electronic structure and optical spectrum o f Cu( C2H4)(22) The u.v.-visible spectrum of (22) has been interpreted in terms of a 4s + 4p excitation of the unpaired electron localized on Cu. Ethylene forms an adduct


w i t h [ C u ( i m i d a z ~ l e ) ~ ] + (23, n=2 b u t n o t 3); revers ib ly form CO adducts .49

however e i t h e r (23, n=2 o r 3) Crystal s t ructures have been determined5' f o r

( C U X ) ~ ( H2C=CHCH2CN) (X=C1 o r Br) and (pentacyclo (1 2.2.2 .Z2 9 526 ' ' .2 l 9 l 3 1 tetracosa-l,5,9,13-tetraene) .AgOTf. I n t e r a c t i o n o f Ag atoms w i t h o l e f i n

matrices has been studied; t ransfer absorption a t 590 nm, was i n the sequence Ag(CH2CH2), < Ag(MeCH=CH2), <

Ag(MeCH2CH=CH&. The lg7Au Mdssbauer spectra have been reported f o r some i so - cyanide and carbene-gold complexes, [LAuCl 1, [L2Aut], [L2Au12'] [L=p-MeC6H4NC, (p-MeC6H4NH)2C: o r p-MeC6H4NH(EtO)C: ] as we1 1 as the methanide complexes52

have been determined fo r c is ,c is- and52 trans, trans- [$-MeC6H4NH( EtO)CI2AuCtO4, -- cis,trans-[p-MeC6H4NH(EtO)CAuC1 3 and [CIAuC=NBut]. 5 3 A secondary ion mass spect ra l study o f Ag(C=NR)4X (X=C104 o r PF6) and [cU(c=NR)4]PF6 has been car r ied

the thermal s t a b i l i t y , as assayed51 by charge-

-

[p-MeC6H4N=C( OEt)AUI3 and [e-MeC6H4N=C( NHC6H4Me-p)AUIn. The Crystal s t ructures

out. 54

2.2 Yl ide complexes. The y l i d e complexes, (24)-(27) have again a t t rac ted considerable at tent ion. Oxidative add i t ion to (24, R=Ph) occurred on react ion w i th ( i ) CC14 [to give (25, X=Y=Cl), (25, X=C1, Y=CC13) and (26, X=Y=X'=Cl, Y'= CC13)1,55a ( i i ) CHBr3 [ t o g ive (25, X=Br, Y=CHBr2)],55b ( i i i ) BrCH2Z (Z=CN o r COPh) [ t o give (25, X=Br, Y=CH2Z)JS5c ( i v ) (RC02)2 (R=Me o r Ph) [to give (25, X=Y=O2CR)ISSdand ( i v ) CH2X2 (X=Br o r I ) [ t o g ive (27); (24, R=Me) reacts ~ i m i l a r l y ] . ~ ~ Other e l e c t r o p h i l i c reagents, HX (X=C1 o r Br ) and AcBr, cleave the AU-C bonds o f (24) to provide XAuCH2PPh2Me (X=C1 o r Br) .57 format ion58 o f polysul phide bridged species S4[Au( CH2)2PPh212Sn[A~( CH2),PPh2I2 (28, n=5) r e s u l t s from i n t e r a c t i o n o f (25, X=Y=Br) w i t h amonium polysulphide. Treatment of (28, n=5) w i t h s o l i d Na2S i n THF provides a small y i e l d o f (28,

n=4); (28, n=4) i s however obtainable i n good y i e l d from (25, X=Y=PhC02) and H2S. A lky la t ion of (27, X=Br o r I) using RLi R=Ph, X=Me, Y=Br) was a lso reported. Reaction o f (27, R=Me, X=Y=I) w i t h MeR21P=CH2 (R'=Me or Ph) gave (27, R=Me, X=Y=CH2?Rl2Me; 21-) from which y l i d e s could be obtained5' on react ion w i t h s t rong base. Various spectral proper t ies of (27, R=Me, X=Y=CH2?Ra2Me, 21-) inc lud ing 'H n.m.r., 1 3 C n.m.r.,m.s. and lg7Au Mssbauer data supported the s t ructure.

(25), M(Au-Au) 163, 132 and 103 cm-l, f o r X=Y=Cl, ,8r OF I r e ~ p . 1 ~ ' s t rucfures h a M been determined f o r (28, != 4 o r 5), (27, R=Ph, X=Y=Me),56 (26, X=X'=Y=Cl, Y'=CC13),55a and (25, X=Y=Cl; X=C1, X=CC13; X=Br, Y=CH2CN; X=Br, X=CH2COPh, X=Y=02CPh; X=Y=02CMe).

The

(27, X=Bu o r Me); (27,

The Raman spectra have been obtained f o r (24) M(Au.. .Au) 64 cm" 1 and o f Crystal

Crystal s t ructures o f o ther y l i d e complexes have a lso been determined, inc lud ing those o f XAuCH2PPh2Me (X=Br o r C1),57 (Ph3P)2CCuC1,61 and (29, X=CH)62

obtained as shown i n Scheme 1. Compound (30, X=CH) reacts w i t h Ph?PAgOClO3 t o


i' (26)

X I

Reagents : i, Ph2PXHPPh2,MezCO,RT; ii, 2$FsAu [THT).CH2CI2

Scheme 1


give [Ph3PAgCH(Ph2PAuPPh2)2CHAgPPh3]2C104-: (31);

been given f o r (29) and (31). AU-C bond towards proton acids i s C6F5-Au; PR3 whi le HC104 o r HBr4 gives [AU(CHR'PR~)~]X (X=C104 o r BF4).

n.m.r. and i .r. data have I n C6F5AuCHR'PR3 complexes,63 the more reac t ive

react ion w i t h HC1 provides C1AuCHR'-

2.3 A1 kynyl and a1 kenyl der ivat ives. (R=Me, E t , Ph o r CF3), prepared from R C S H , Ar3PAuC1 and NaOEt, have been studied. 6 4 a

Ph3PAuCXPh (Au ... Au 3.379 I), as wel l as the more complex, polynuclear species6' [ A U ~ P ~ ( C ~ C B U ~ ) ( P P ~ ~ ) ~ I [AU(C:CBU~)~] ( l i n e a r anion) and [Au~A~, (C&P~) , (PP~~)~ ]

(32). I n (32), produced from Ph3PAuC-CPh and [Ag(CXPh)l o r Ph3P and [AuA~(CECP~)~],, there i s a l i n e a r arrangement o f 2PhCrC groups about each Au w i t h each Ag asymnetrical ly .rr-bonded to two CZC u n i t s and to a Ph3P.

(E)-CF3CF=CF, '(z)-CF3CC1=CF, CF3CPh=CF] RFX ( X = I o r Br ) on successive treatment w i t h Cd o r Zn i n DMF and w i t h CuX. The overa l l scheme occurs w i th re ten t ion o f conf igurat ion. reagents,stable a t room temperature i n the absence o f O2 o r moisture, undergo reactions w i t h organic hal ides.66

Ligand-exchange reactions o f AP3PAuC%CR

Crystal s t ructures have been determined f o r the simple

tl

Per- and po ly - f luorov iny l copper compounds, RF-CU [e.g. RF=CF2=CF, ( I ) - o r have been prepared i n high y e l d from

The v iny copper

2.4 Alky l der ivat ives. provides (Me2AuNH tr imer, which i s i n a cha i r c ~ n f o r m a t i o n . ~ ' Formation, n.m.r. spectra and d issoc ia t ion o f Me2Au1V-nucleosides have been studied. 6a Select ive reduct ive e l im ina t ion o f R-Me from e-[Me2AuR(PR3)1 takes place f o r R=alkenyl o r a r y l whereas on ly &-Me i s formed when R=alkynyl o r an e lect ron withdrawing group.69

"F N.m.r. spectra and syntheses have been reported" f o r CF3Cu (from the t ransmeta l la t ion react ion o f t r i f luoromethy l -z inc o r -cadmium w i t h CuX), CF3Ag and (CF3)3Au (by co-condensation a t -190°C o f CF3' w i t h M vapours). s i n g l e t (6 -28.8 ppm r e l . to CFC13) i s observed i n the ''F n.m.r. spectrum o f CF3Cu i n DMF a t -5O"C, wh i le a t RT, two resonances f o r CF3Cu compounds ( a t -32.3 and -35.5 ppm) are seen as we l l as those f o r CF3CF2Cu ( 6 -84.7 and -113.7 pprn). The compound, (CF3)2CFAg(MeCN) (33), obtained from AgF and CF3CF=CF2 i n MeCN, undergoes d ispropor t ionat ion i n so lu t ion (equation 2); values o f K are so lvent dependent. have .been determined. 'I1

The reac t ion o f (Me2AuI)2 w i t h KNH2 i n l i q u i d NH3

NH2 groups br idge Me2Au u n i t s to g ive a six-membered Au3N3 r ing , (n=3 o r 4); i n the c r y s t a l s t ruc tu re o f the more s tab le

2)n

Only a

eq Crystal s t ructures o f (33) and [Rh(dppe)2J [ ASCF(C~;)~I

2[(CF3)2CFAg.MeCN] Keel Ag+(solv) t [AgCF(CF3)21- (2)


I I11 2.5 Aryl der ivat ives. compl exes has been prepared , i ncl ud i ng tg-02NC6H4AuL I (34), and trans- and cis-[o-O2NC6H4AuCl2(PPh3) 1. l i n e a r complex (34, Ln=Ph3As) ind icated no Au. ..O intramolecular co-ordination. ''

Also ~ y n t h e s i z e d - ~ ~ were AuI1* complexes conta7ning the chelat ing a r y l group g-Me2NCH C H

[ f i - M e 2 ~ ~ 1 f ~ N ~ p e A u 1 C 1 lC104 and [g-Me N * A W - g ] C l O 4 as we1 1

t g - P h N ~ u ~ M e , - g I [AuCl41 (36). The feature i n the c rys ta l s t ruc tu re of (35, R=Ph).CH2C12 i s square pyramidal co-ordination t o Au (one N o f phen i s a x i a l ) i n cont rast t o square planar Au i n (36). a mono- o r h i -dentate l igand as demanded by the s i tua t ion .74

I Various pentahalophenyl der iva t ives o f Au and AulI1 have been produced, inc lud ing complexes invo lv ing the l igands ( i ) , 7 5 Ph2P(S)CH P(S)Ph [ ( ArF&GPPh ) CH21 , [( ArF)3AuSPPh2CH2P( S) Ph21, [ (Ar~)~&i:i 04 and [ (ArF),A!&$HPPh2S] , (i i ) '' Ph2P(S)NHR(S)Ph2, ( i i i ) Ph2PCHPPh2Me, 3. 7 6

[(At- ) AuPh2PCHPPh2Mel (a=l o r 3), [ (Ar ) Au{Ph2PCH(PPh2Me)}AuXn], m=l o r 3; X F!!! F m 'ArF, m=l o r 3; X=C1, n=l and [{Ar+uPh2PCH(PPh2Me)12M]X (M=Ag o r Au). ( i v )

Ph2PNHPPh2( DPPA) 7 7 e . ~ . [ArAu( DPPA)AuArI, [ A r Ar), (ArF)3Au(DPPA)AuX (X=C1 o r ArF), ArX/'p''I?D?PA)/+uI'XAr (37, X=C1 o r Br) and ArX2Au(DPPA)AuAr (X=C1 o r Br) [ArF=C6F5; Ar=C6X5 (X=C1 o r F ) ] . Crystal s t ructure d e t e r m i n a t i ~ n ~ ~ revealed a Au-Au bond o f length 2.576(2) fi i n (37,X=C1).

The c rys ta l s t ruc tu re o f [ C U ~ ( ~ - X - ~ - M ~ C ~ H ~ ) ~ B ~ ~ ] (X=4,4-Me2-2-oxazolinyl ) has been deter~nined;~ ' the s i x Cu form a d i s t o r t e d octahedron w i th br idg ing a r y l and B r . Each ary loxazol ine s u b s t i t u t e n t i s co-ordinated via the ips0 C

to two Cu and y& N to a t h i r d Cu. U.V. ) o f 1,1,1' ,1 '-(Ph3PAu)4-ferrocene b is te t ra f luoroboratehave been reported. 79

A number o f neutra l and anion ic g-02NC6H4'AU and -Au

[2-O2NC6H4AuCN I - !I* An X-ray d i f f r a c t i o n study o f the

[ g - M e 2 m u ( p h e n ) P R I [BF 1 (35)

as74 the mixed d iary1 compounds, [g-PhN=NC6H4 d=?I uC6H4CH2 Me2-g(C1 ),I and cis-

The g-PhN=NC6H4 group acts as

X,Au( DPPA) 1 (c=O o r 1, X=C1 o r

Synthesis and spectra ( 'H n.m.r., i.r. and

R e f

1. 2.

3 .

4. 5.

6. 7.

8.

erences

P. Boudjouk, R, Sooriyakumaran, and B.-H. Han, J. Org. Chem., 1986, 51, 2818. G.R. Stevenson and R.T. Hashim, J. Phys. Chem., 1986, 90, 1896; see a l s o G.R. Stevenson and M.A. Nebgen, J. Am. Chem. SOC., 1986, 108, 5509. T. Lindvai, T. F r i e d l , H. Butenschh , T. Clark and A. de Meijere, Angew. Chem I n t . Ed. Engl., 1986, 25, 719; Y . Cohen, J. Klein, and M. Rabinovitz, J. Chem. SOC., Chem. Commun., 1986, 1071; R. Benken, K. F inne i se r , H. von Puttkamer, H. G h t h e r , B. Eliasson,and U. Edlund, Helv. Chim. Acta, 1986, 69, 955. L. Manceron, M.Hawkins, and L. Andrews, J. Phys. Chem., 1986, 90, 4987. 0. Ayed, A. L o u t e l l i e r , L. Manceron, and J.P. Perchard, J. Am. Chem. SOC., 1986, E, 8138; D. P l avs i c , D. S r z i c , and L. Klasinc, J. Phys. Chem., 1986, 90, 2075. B. Tecle', A.F.M.M. Rahman, and J.P. O l ive r , J. Organomet. Chem. , 1986, 317, 267. N.H. But t rus , C. Eaborn, P.B. Hitchcock, J.D. Smith, J . G . Stamper, and A.C. Su l l i van , J. Chem. SOC., Chem. Commun., 1986, 969.

B. S i l v i , 0. Ayed, and W.B. Person, w., p.848.


9. N.H. Bu t t rus , C. Eaborn, S.H. Gupta, P.B. Hitchcock, J . D . Smith,and

10. G.W. Klumpp, P.J.A. Geurink, N.J.R. van E. Homes, F.J.J. de Kanter, M. Vos,

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19. H.-J. Gais, I. Erdelmeier, H . J . Lindner, and J. Vollhardt , Angew. Chem. I n t .

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23. H. D ie t r i ch , W. Mandi, and R. Knorr, J. Am. Chem. SOC., 1986, 108, 2462. 24. G. Vanerman, M. van Beylen, and P. Geerl ings, J. Phys. Chem., 1986, 90, 603. 25. R.B. Bates and T.J. Siahaan, J. Org. Chem., 1986, 2, 1432;

26. D. Hoel l , J. Lex, and K. Mullen, J. Am. Chem. SOC., 1986, 108, 5983. 27. R. Hacker, P. von R. Schleyer , G. Reber, G. wller, and L. Brandsma,

28. (a) M. Marsch, W. Massa, K. Harms, G. Baum, and G. Boche, Angew. Chem. I n t .

A.C. Su l l i van , J. Chem. SOC., Chem. Commun.,1986, 1043.

and A.L. Spek, R e d . Trav. Chim. Pays-Bas, 1986, 10, 398.

1986, 119, 1331.

Ed. Engl., 1986, 2, 938.

J. Am.' Chem. SOC., 1986, 108, 3415.

B. Gordon and J .E . Loftus , M., p.1618.

J. Organomet. Chem., 1986, 316, C4.

Ed. Engl., 1986, 25, 1011; (b) G. Boche, M. Marsch, and K. H a r m s , M., p.373.

29. P.J. Crowley, M.R. Leach, 0. Meth-Cohn, and B . J . Wakefield, Tetrahedron L e t t . 1986, 27, 2909.

30. J.L. Mooney, 2. Marcinow, and P.W. Rabideau, J. Org. Chem., 1986, 51, 527; see a l s o , P.W. Rabideau, A . J . Maxwell, and A. Sygula, u., p.3181.

31. M.J . K a m l e t and R.W. Ta f t , Acta Chem. Scand., Ser. B, 1986, 40, 619. 32. H.P.S. Chauhan, H. kawa, and R.J. Lagow, J. Org. SOC., 1986, 51, 1632. 33. S. Gronert and A. S t r e i t w i e s e r , J. Am. Chem. SOC., 1986, 108, 7016. 34. G.W. Klumpp and M.J . S innige, Tetrahedron L e t t . , 1986, 27, 2247. 35. W. Bauer, G. Muller, R. Pi, and P. von R. Schleyer , Angew. Chem. I n t . Ed.

36. A.L. Campbell and I . K . Khanna, Tetrahedron L e t t . , 1986, 2, 3963. 37. J.P. Gildey and D.A. Widdowson, Tetrahedron Lett.,1986, 27, 5525;

38. G.E. Herberich, B. Hessner, and M. Hos ta l ik , Angew. Chem. I n t . Ed. Engl.,

39. G. Fraenkel, Polym. Prepr . (Am. Chem. SOC., Div. Polym. Chem.), 1986, 27,

40. ( a ) A. Maercker, T. Graule, and U. Girreser, Angew. Chem. I n t . Ed. Engl.,

Engl., 1986, 2, 1103.

J. Chem. SOC., Chem. Commun., 1986, 1235.

1986, 25, 642.

132 (Chem. Abs., 1986, 105, 208981).

1986, 2, 167; (b) P. von R. Schleyer , E. Kaufmann, A.J . Kos, T. C l a r , and J . A . Pople, w., p.169.

E.-I. Negishi and T. Takahashi, J. Am. Chem. SOC., 1986, 108, 3462; ( c ) H. K l e i j n and P. Vermeer, J. Organomet. Chem., 1986, 302, 1; (d) F. Matta, R. Betz, B. Schmid, and R.R. Schmidt, Chem. B e r . , 1986, 119, 472.

41. ( a ) B.L. Chenard and C.M. von Zyl, J. Org. Chem., 1986, 2, 3561; (b)

42. J. Barluenga, J.R. Fernandez, and M. Yus, J. Chem. Res. (S), 1986, 273. 43. C. Schade, P. von R. Schleyer , M. Geissler, and E. Weiss, Angew. Chem. I n t .

Ed. Engl., 1986, 2, 902. 44. ( a ) H. Hartkorn, F.H. Kuhler, G. Muller, and G. Reber, Angew. Chem. I n t . Ed.

Engl., 1986, 25, 468; (b) P. von R. Schleyer , E. Kaufmann, A.J . Kos, H. Mayr, and J. Chandrasekhar, J. Chem. SOC., Chem. Commun.,1986, 1583; (c) M. C h r i s t 1 and D. B r k k n e r , Chem. Ber., 1986, 119, 2025.

45. R.T. McDonald and S. Bywater, Organometallics, 1986, 5, 1529.


46. H. - J . Gais, J. Vollhardt , and H . J . Lindner, Angew. Chem. I n t . Ed. Engl.,

47. H. Gunther, D. Moskau, R. Dujardin, and A. Maercker, Tetrahedron L e t t . ,

48. P. von R. Schleyer , E. Kaufmann, G.W. Bpi tznagel , R. Janoschek, and

49. G. Nicolas and J . C . Ba r the l a t , J. Phys. Chem., 1986, 90, 2870; S. Kitagawa

50. P. Yu. Zava l i i , M.G. Mys'kiv, and E . I . Gladyshevskii, K r i s t a l l o g r a f i y a ,

1986, 25, 939.

1986, 27, 2251.

G. Winkelhofer, Organometallics, 1986, 5, 79.

and M. Munakata, Bul l . Chem. SOC. Jpn., 1986, 2, 2743,2751.

1986, 31, 88 (Chem. Abs., 1986, 105, 209077); J.R. Matz, J . C . Clardy, and J. Mitchel l , J. Am. Chem. SOC. , 1986, 108, 515.

J .E . McMurry, G . J . Haley,

51. M.P. Andrews and G.A. Ozin, J. Phys. Chem. , 1986, 90, 2922. 52. G. B a n d i t e l l i , F. Bonat i , S. Calogero, G. Valle, F.E. Wagner, and R. Wordel,

53. D.S. Eggleston, D.F. Chodosh, R.L. Webb, and L.L. Davis, Acta Crys t a l log r . ,

54. L.D. Detter, R.G. Cooks, and R.A. Walton, Inorg. Chim. Acta, 1986 ,115 , 55. 55. (a) H.H. Murray, J.P. F rack le r , L.C. P o r t e r , and A.M. Mazany, J. Chem. Soc.,

Chem. Commun., 1986, 321; (b) H.H. Murray and J.P. Fackler , Inorg. Chem. Acta, 1986, 115, 207; (c) H.H. Murray, J.P. Fackler , A.M. Mazany, L.C. P o r t e r , J.S. Hain, and L.R. Fa lve l lo , m., 1986, 114, 1 7 1 ; (d) L.C. P o r t e r and J.P. Fackler , Acta Crystal logr . ,Sect . C, '1986, 42, 1128,1646.

Organometallics, 1986, 5, 1652.

1986, 42, 1125; H.C. Knachel, C.A. De t to r r e , H . J . Galaska, T.A. Salupo, J.P. Fackler , and H.H. Murray, Inorg. Chim. Acta, 1987, 126, 7.

Organometallics, 1986, 5, 1346.

Sect. C, 1986, 42, 36.

56. H. Schmidbaur, C. Hartmann, J. Riede, B. Huber, and G. Wl l e r ,

57. L.C. P o r t e r , H. Knachel, and J.P. Fackler , Acta Crys t a l log r . , Sect . C ,

58. J.P. Fackler and L.C. P o r t e r , J. Am, Chem. SOC. , 1986, m, 2750. 59. H. Schmidbaur and C. Hartmann, Angew. Chem. I n t . Ed. Engl., 1986, 25, 575. 60. R.J.H. Clark, J .H. Tocher, J.P. Fackler , R. Neira, H.H. Murray, and

61. G. Nller, C. Kruger, C. Zyb i l l , and H. Schmidbaur, Acta Crys t a l log r . , See.

62. x. Uson, A. Laguna, M. Laguna, M. C. Gimeno, P. G. Jones , C. F i t t s chen , and

63. R. Uson, A. Laguna, M. Laguna, and M.C. Gimeno, Inorg. Chim. Acta, 1986, 114, 64. (a) R.J . Cross and M.F. Davidson, J. Chem. SOC. Dalton. Trans., 1986, 411;

65. O.M. Abu-Salah and C.G. Knobler, J. Organomet. Chem., 1986, 302, C 1 0 ;

H. Knackel, J. Organomet. Chem., 1986, 303, 437.

C , 1986, 42, 1141.

G.M. Sheldr ick, J. Chem. SOC., Chem. Commun., 1986, 509.

91.

(b) M . I . Bruce and D.N. Duffy, Aust. J. Chem., 1986, 3, 1697.

D.E. Smith, A . J . Welch, I. Treurnicht , and R. J . Puddephatt, Inorg. Chim. Acta, 1986, 25, 4616.

66. D. J. Burton and S.W. Hansen, J. Am. Chem. SOC. , 1986, 108, 4229. 67. U. G rhs l e and J. S t r l h l e , Z. Anorg. Allg. Chem., 1985, 531, 26. 68. Y. Mizuno and S. Komiya, Chem. L e t t . , 1986, 1477; Inorg. Chim. Acta, 1986,

69. T K o m i y a , S. Ozaki, and A. Shibua, J. Chem. S O C . , Chem. Commun., 1986, 1555. 70. D.M. Wiemers and D . J . Burton, J. Am. Chem. Soc., 1986, 108, 832;

M.A. Guerra, T.R. Bierschenk, and R . J . Lawow, J. Organomet. Chem., 1986, 307, C58.

125, L13.

71. E. Burch and J . C . Calabrese, J. Am. Chem. Soc., 1986, 108, 5359. 72. J. Vicente, A. Arcas, M. Mora, X. Solans, and M. Font-Altaba, J. Organomet.

Chem. , 1986, 309, 369. 73. J. Vicente, M.T. Chicote , M.D. Bermudez, P.G. Jones, C. F i t t s chen , and

G.M. Sheldr ick, J. Chem. Soc., Dalton Trans, 1986, 2361. 74. J. Vicente, M.T. Chicote, M.D. Bermudez, M . J . Sanchez-Santano, P.G. Jones,

C. F i t t s chen , and G.M. Sheldr ick, J. Organomet. Chem., 1986, 310, 401. 75. A. Laguna, M. Laguna, A. Rojo, and M.M. F r a i l e , J. Organomet. Chem., 1986,

315, 269. 76. T U s o n , A. Laguna, M. Laguna, I. Lazaro, A. Morata, P.G. Jones, and

G.M. Sheldr ick, J. Chem. Soc., Dalton Trans, 1986, 669.


77. R. Uson, A. Laguna, M. Laguna, M.N. F r a i l e , P.G. Jones, and G.M. Sheldr ick,

78. E. Wehman, G. von Koten, and J.T.B.H. J a s t r z e b s k i , J. Organomet. Chem. , 79. E.G. Perevalova, T.V. Baukova, M.M. Sazonenko, and K . I . Grandberg,

J. Chem. SOC., Dalton Trans., 1986, 291.

1986, 302, C35.

Bull. Acad. Sci . USSR, Div. Chem. Sc i . , 1985, 34, 1726.

Bib l i o grap hy

The fol lowing r e fe rences do .not appear i n t h e main t ex t .

A l k a l i Metals

N. S. Mills and A.R. Rusinko, J. Org. Chem., 1986, 51, 2567. Dianions from Me2C=CMe2 using BuLi.TMED o r BuLi.ButOK.

S. Cabiddu, C. F l o r i s , and S. Melis, Tetrahedron L e t t . , 1986, 27, 4625. D i l i t h i a t i o n of a r y l t h ioe the r s .

V. Cere, C. Paolucci , S. P o l l i c i n o , and E. San id r i , J. Chem. SOC., Chem. Commun., 1986, 223. Acid c a t a l y s i s i n the intramolecular a d d i t i o n of a - l i t h iosu lphox ide t o i s o l a t e d double bonds.

J . N . Bonfigl io , J. Org. Chem., 1986, 51, 2833. or tho-Lithiat ion of a l k y l arenesulphonates .

D.L. Comins and J .D. Brown, J. Org. Chem., 1986, 2, 3566. o r tho -L i th i a t ion of PhCONEtCH2CH2NEt2.

R.R. F ra se r and S. Savard, Can. J. Chem., 1986, 64, 621. o r tho -L i th i a t ion of 1-cyanonaphthalene.

P. Beak and K.D. Wilson, J. Org. Chem., 1986, 51, 4627. l i t h i a t i o n of a,B-unsaturated amides.

Directed @'-

H.J. Scholz and H. Werner, J. Organomet, Chem., 1986, 303, C8. Syn thes i s of L i2 (C5Me4) 2CH21 . P.A. Brown and P.R. Jenkins , J. Chem. SOC., Perkin Trans. 1, 1986, 1129. Formation of CH2=CH-CLi=CHZ.

S.M. Bachrach, J. Am. Chem. SOC., 1986, 108, 6406. cyclobu tane.

Copper, S i l v e r and Gold

R. Uson and A. Laguna, Inorg. Chim. Acta, 1986, 122, 81.

Y. Yamamoto and H. Konno, Bull. Chem. SOC. Jpn., 1986, 2, 1327. X-ray p.e. s p e c t r a of (Ph PCH2)2MC1 (M=Cu o r Au).

O.M. Abu-Salah, A.R. Al-Ohaly and H.A. Al-Qahtani, Inorg. Chem. Acta, 1986, 17, L29. [Ag(C-C)Ph)2]- and Ag[Cl(C-CPh) I-.

Ca lcu la t ion on 1,3-Liz-

(C6C15)3Au111 complexes.

3

Y. Yamamoto, Angew. Chem. I n t . Ed. Engl., 1986, 25, 947. and RCu.A1C13.

Review on RCu.BF3

M.B. Kuzminskii, A.A. Bagatur 'yants , and V.B. Kazanyskli, Bul l . Acad. Sci . USSR, Div. Chem. Sc i . , 1986, 35, 260.

I. Fleming and F.J. Pul ido, J. Chem. SOC., Chem. Commun., 1986, 1010. S i ly l - cupra t ion of a l l e n e s .

I. Fleming and A.P. Thomas, J. Chem. SOC., Chem. Commun., 1986, 1456. Reactions of s i l y l cupra t e s with a l l y 1 a c e t a t e s o r urethanes.

S.H. Ber t z and C.P.Gibson, J. Am. Chem. SOC., 1986, 108, 8287. .D i f f e ren t products of ox ida t ion of RR' (CN)Li2Cu compared t o RR'CuLi.

Ab i n i t i o c a l c u l a t i o n on CuCO and CuCoS.

Group II: The Alkaline Earths and Zinc and its Congeners

BY J. L. WARDELL 1 Beryllium

Observation of p a r t i a l l y relaxed coupling to 'Be i n the 1 3 C n.m.r. spectrum of Cp2Be i n solution leads to an estimate of 10" s-' for the r a t e of molecular inversion. and C2Bep have been investigated by ab i n i t i o methods employing second onder Wller -P lesse t perturbation theory and, f o r the triatomic species, CASSCF techniques.2

reagent and BeC12) has been shown4 to enantioselectively reduce prochiral ketones [s PhCOR' ( t o (?)-a1 kyl phenyl carbi no1 s ) and R"C COR' ( t o (!)- alcohols)] . beryl 1 i um compounds o r R2Be.

2' Ye The s t ruc tures and energi es of s i n g l e t and tri pl e t CBe

Ab i n i t i o methods3 have also been used on H3P=CHBeH and C3H3BeH. (J)-2-Methylbutylberyllium chloride (RBeC1,prepared from the Grignard

Results have been compared w i t h those obtained u s i n g cis-myrtanyl-

2 Magnesium

The isomerization of alkyl groups during Grignard formation, from Mg metal and RX i n Et20, is accepted to occur through intermediate alkyl radicals. A quantitative treatment of radical isomerization indicated t h a t the intermediate radicals diffuse f ree ly i n solution rather than being absorbed on the Mg surface. Mg provides both the unrearranged Grignard, RMgBr, (1 ) and CH2=CH(CH2)2CHPhF'gBr

( 2 ) . a r i ses from rapid rearrangement of R. during the process of Grignard reagent formation. single crystal surface leads to the formation of a surface bromide and gas-phase hydrocarbons,' including ethane. Stable surface a1 kyls were not observed even a t -150°C. Vapours of Mg and Ca have been co-deposited' w i t h MeX (X=I, Br, C1 F o r H ) i n argon a t 9 K. I t was concluded f o r the metal atoms and metal c lus te rs [Mga ( ~ = 1 - 4 , x); Can (%=1,2,x)] that: reactive than atoms, ( i i ) la rger c lus te rs a re more reactive than smaller ones, ( i i i ) calcium species a re more reactive than magnesium species and ( i v ) the reactivityof CH3Xis i n the sequence X = I > F > Br > C1.

Syntheses have been reported' f o r ( i ) RCH(MgBr)2 ( R = H or Me3Si), from RCHBr2 and Mg/Hg i n Pr120 a t RT, ( i i ) (Et0)2P(0)CH2MgX [from (Et0)2P(0)CH21 and

[For references see page 21

Reaction of cis- or trans-2-Ph-cyclobutylmethyl bromide (RBr) w i t h

Although rearrangement of (1) to ( 2 ) can occur, i t was concluded t h a t ( 2 )

Chemisorption and subsequent decomposition of MeBr on a Mg(OOO1)

( i ) larger c lus te rs a re more

14

Group IZ: The Alkaline Earths and Zinc and its Congeners 15

R-MgBr ( i n a 64% y i e l d ) i n Et20 from R-Br, were R-H and R-CH2CH20Et (R=l -adamantyl ) .

Chelated compounds, Mg[(CH2),,YRR’12 (3, g=3 have been prepared from the ZrC14 catalyzed add alkenyl-amines and ethers. lo The spectra (m.s

Pr’MgCl i n THF a t -7O”C], ( i i i ) MeP(CH2C6H4MgBr-~)2 and ( i v ) l-adamantyl- magnesium bromide.’ Addit ional products, obtained dur ing the preparation o f

R-OH (from traces o f 02), R-R

o r 4) and M [(CH2I40Rl2 (41, t ions of MgH2 t o appropriate , ’H n.m.r., 1 3 C n.m.r., and i . r . )

o f (3) and (4 ) as wel l as the c rys ta l s t ruc tu re o f (3, n=3, R=Me) have been reported. A t low temperature, the methyl groups i n (4, R=Me) have d i s t i n c t resonances i n the 1 3 C n.m.r. spectrum. determined f o r ( i ) [EtMg(CH ) NR R l2 (5 , 5=3, R1R2=Me obtained from Et2Mg and (3), ( i i ) ” tk5H4C(SiMe3)2’C(SiMe3)2C5H4 (6, M=Mg) and ( i i i ) 1 3 [BuSMg{p-N(SiMe ) 11 2.118(4) 8.) BuMgBu’ w i t h g-(Me3Si)2CH-pyridine and (Me3Si)2NH respect ive ly . CH2=CH2, RR’COand C02), spectra and thermal s t a b i l i t y o f (5 ) have a lso been reported.

The f ree energy o f r o t a t i o n about the C=C bond i n the aza-al ly1 metal der ivat ive, CHZ=CHNcyM (8, M=MgEt) has been estimated t o be 14.520.3 k ca l m - l a t 0°C i n hexane from ’H n.m.r. data; and 14.2k0.8 K cal mol-’ fo r M=Li, [A1Et3 -,LitJ and ZnCl respectively. ’“ Use o f 25Mg n.m.r. spectroscopy has been made i n determining complexing a b i l i t i e s o f donors, L, t o Cp2Mg (9); > PMe > Et20 > N E t 3 = PhOk = Pr120. and R2Mg [g. R2=(Et0)2, Et2, (~ I ’ -CH~=CHCH~)~ o r -CH2CH=CHCH2-I. c rys ta l s t ruc tu re determination o f (Cp M s O E ~ ) ~ revealed a M404 core ( lo). ’ ’

non- o r slowly enol izable esters o r carboxamides i n t o 2-propenyl ketones.

The use o f Mg(OCH2CH20Et)2 i n s o l u b i l i z i n g RNa (R=alkyl o r a lkeny l ) i n a l i p h a t i c hydrocarbons has been i l l u s t r a t e d . P a r t i c u l a r l y thermally s tab le complexes are

obtained w i t h 1 :1 r a t i o s o f RLi:Mg(OCH2CH20Et)2; t h e i r meta l la t ing and reducing a b i l i t i e s (9. towards Ph2CO) have been studied.16 detected” i n the Grignard react ions w i t h Ph2C0 and w i t h PhCOCOPh.

case, two rad ica l species were detected, e.~. i n the PhCOCOPh reactions, a purple-coloured [(PhCOCOPh)-’, RMgBrt12, and golden-coloured, [ ( PhCROMgBr .COPh)-’- RMgBrtI2. the PhCH=CHCH2C1-RMgX reactions, which provide a1 k y l a t i o n and d imer isat ion products . *

Crystal s t ructures have a lso been 1 2 Me, cyclohexyl),”

?--7 2 n

(7) (Mg2N2 core w i t h Mg-C 2.08(1) and Mg-N 3 2 2 Compounds ( 6 ) and (7) have been synthesised by the react ion o f

Reactions ( w i t h

values f o r o ther (8, M) are 17.7, x19

sequence obtained was L=TMED > THF > DME > dioxane Compounds, CpMgR, can be formed from ( 9 ) 3

The

The combination, CH2=CHCH2MgBr-LiNR2, has been found useful i n conver t ing

Free rad ica ls have been I n each

Both nuc leophi l ic subs t i tu t ions and s.e.t. processes operate i n


c

c

( 3 , n = 3 , R,R'=Me)

b ( 6, M = Mg)

oc O H

C

C

( 4 , R - M e )

b

c

(171

Group II: The Alkaline Earths and Zinc and its Congeners 17

3 Calcium and Strontium

Co-condensat i~n '~ o f Ca atoms and A r H vapours a t 77K provided (ArH-.)2Ca2+ (Ar=H, PhMe, PhEt o r PhSiMe3). vapourizing Ca a t 900°C i n a vacuum vessel,20 have been successful ly used t o prepare organocalcium compounds i n THF from organic bromides, iodides and a l k y l ch lor ides. Gas phase react ions o f M vapour (M=Ca o r Sr) w i t h cyclopentadiene produced CpM, which has been invest igated using laser spectroscopy." The gas phase molecular s t ruc tu re determination o f (C5Me5)2p (Cp, Cd), obtained from Cp*H .and Ca12, by e.d. revealed" tha t the two Cp r ings are n o t p a r a l l e l ;

i n cont rast those i n Cp2 Mg.

Calcium u l t r a f i n e par t i c les , obtained by

*

4 Zinc and Cadmium

MNDO ca lcu lat ions have been performed on organozi nc compounds .2 Synthesis o f (CF3)2M (M=Zn o r Cd) has been obtained from react ions o f the

meta l vapour w i t h CF3; obtained from CF3CF3 by low temperature rad io frequency discharge o r plasma. s t a b i l i s e d on complexation w i t h donors such as pyr id ine and g l y ~ n e . ~ " ~ a1 te rna t ive t o (CF3)2Cd involves the t ransmeta l la t ion react ion o f Me2Cd and excess (CF3)2Hg i n glyme. The "F n.m.r. spectra were recorded. use24c o f Cd powder and RFI i n DMF has been made i n the formation o f RFCdI and RF Cd.

t h a t the monomeric compounds contain te t rava len t M w i t h M-N i n t e r a c t i o n becoming progressively weaker (and CMC angles becoming la rger ) i n the sequence M=(Mg>)Zn >

Cd(>Hg): 2.49 8 (174") (6, M=Cd); 2.78 8 (180") (6, M=Hg); corresponding average M-C bond lengths are 2.22, 2.27, 2.27, and 2.16 8.

(C5H4SiMe3)2Zn (12) (from the Na analogues and ZnC12) have been d e ~ c r i b e d . ~ ' I n both (11) and (12), one r i n g i s 17' bound w i t h the other rl'; Me3Si subst i tuent i n the q'-bound r i n g i s attached to the carbon bonded t o Zn. ind ica te f lux iona l s t ructures i n so lut ion.

R'CH(ZnBr)M,M=Li I , R'CH(ZnBr)CuCNM (M=MgBr o r L i ) , R'R2ZnM (M=MgX o r L i ) (14) have been studied. (14) towards 2-cyclohexen-1-one i s R'=Me2PhSi > CH2=CH > Pr',Bu,Et > Bu' > Ph Me,But >> ButCH2 - a d i f f e r e n t sequence from t h a t obtained from RR'CuM. y i e l d i n g and s tereospeci f ic Reformatsky react ions a t low temperatures are obtained'' from XCHRC02Et (X=C1 o r Br ) , c y c l i c ketones and laminated Zn/Ag- graphite, obtained from C8K and ZnC12/AgOAc i n THF ,

Unsolvated compounds are unstable a t RT bu t are An

The

The c rys ta l s t ruc tu re determinations o f (6, M=Zn o r Cd) have ind icated"

9. M-N(CMC) = 2.13 8 (157") (6, M=Mg); 2.30 1 (164") (6, M=Zn);

The syntheses and e lect ron d i f f r a c t i o n s t ructures o f (C5Me5)2Zn (11) and

N.m.r. spectra

Synthetic uses o f the mixed metal compounds CH2=CHCHR'CH(ZnBr)M [13, (13) and CuCN, and

The r e a c t i v j t y sequence:' R' i n

High

High enant ioselect ive


addit ions (up to 99% x.) o f R2Zn t o RCHO occurs29 using (-)-(3)-=-(Me2N)-

isoborneol, as a c h i r a l a u x i l i a r y to a c t i v a t e the R2Zn. products o f reac t ion o f Et2Zn w i t h t r i h y d r i c phenols i n THF and dioxane have been

investigated. 3 0

The k i n e t i c s and

5 Mercury

5.1 General. The e f f e c t s o f subs t i tu t ion on the n.m.r. spectra, especia l ly

the chemical sh i f t s , o f organomercurial s have been var ious ly investigated; 3 1

series looked a t inc lude Ar2Hg ( 1 3 C and lg9Hg), PhHgN(S02Ph)R ('"Hg), ArHgCZ- CC6H4F-p and RC-CHgC6H4F-p ( lg9Hg and "F), as wel l as ArHgN(S02Ph)C6H4F and ArHgC6H4F ("F).

using "F n.m.r. Equ i l ib r ia , equation 1, i n DMSO and PhMe, have been stud ied3*

cyHgCXC6H4F-e + Q-X C, CyHgX + Q-CECC6H4F-e (1 ) Q=H, PhHg, Ph3Pb o r Ph3Sn; X=SPh o r N(S02Ph)Ph

5 .2 n-Complexes . n-compl exes [ArH=C6MeQH6-d] i n CH2C1 a t low temperature . The complex, C6Me6:Hg(02CCF3)2 (15) was iso la ted and' i t s c rys ta l s t ruc tu re determined. 33a

On i r r a d i a t i o n a t the C-T band, (15) was transformed to C6Me5CH2Hg02CCF3.

ac t iva t ion o f A r H i n mercurations proceeds via n-complexes: quant i ta t i ve spectrophotonetr ic analys is o f the formation constants o f the n-complexes and the 2nd order r a t e constants es tab l i sh t h a t H s ( O ~ C C F ~ ) ~ i s the reac t ive e lec t ro - p h i l i c species, both i n n-complexation formation and i n the aromatic subst i tu t ion. 3 3 b

Charge t rans fer spectra have been observed f o r ArH:Hg(02CCF3)2

The

5 . 3 Methylmercury complexes. Various methylmercury complexes have been

invest igated by spectroscopy (%. v i b r a t i o n and n.m.r.) and/or by c r y s t a l l o -

graphy. The complex between MeHgN03 and 2,6-[MeCHPh(pyridin-2-y1 )I2 pyr id ine, L, can be separated i n t o 9- and =-forms. The c rys ta l s t ruc tu re o f [ M e H g ( E - L ) lN03.2H20 consis ts o f ;B te t racoord inate Hg bonded most s t rongly t o the centra l N o f the t r iden ta te l igand: (Hg-N 2.283(9) 8);other Hg-N are 2.546(11) and 2.595(10) 8 .

MeHg i s bonded t o N;

in te rac t ion . The v ib ra t iona l spectra o f (16, R=Me o r H) suggests t h a t the Hg-N

i n t e r a c t i o n pers is ts i n aqueous so lu t ion over a range o f pH complexes, MeHgfiH2CH2CONHCH2C0 - (1 7) and [MeHgNH2CH2CONHCH2HgMe]C104, have been

obtained from g l y c y l g l y ~ i n e ; ~ ~ ~ bonding o f Mehg t o N occurs i n both the s o l i d

s ta te and i n so lut ion.

I n MeOH, L appears t o be a t leas t b i d e t ~ t a t e . ~ ~ I n the c r y s t a l of the MeHg' complex o f alanine, MeHg6H2CHRCO2- (16, R=Me),

there i s an addi t ional weak Hg .... 0 intramolecular

The

Several MeHg' complexes w i t h the adenine l igand [(18, X=CH) H-Ad] have been


i so la ted : j6 a l l contain MeHg-N l inkages. Complexes obtained are: ( i ) [(MeHg)2(Ad-H).lEtOH (b ind ing a t N6 and Ng t o a di-deprotonated adenine moiety),

( i i ) [(MeHg)3(Ad-2H)1.1H20 (b ind ing a t N6, N6 and Ng), ( i i i ) [(MeHg)3(Ad)l(N03)2. H20 (binding a t N3, N7 and Ng), ( i v ) {[(MeHg)2(Ad)l[(EleHg)3(Ad)l)(N03)3.3H20 (binding i n [(MeHg)2(Ad)lt t o N7 and Ng: pa i rs of complimentary N6-H.. .Nf bonds) and (v ) [(MeHg)4(Ad-2H)l NO3 (b ind ing

a t N3, NgF Hs and'Ng), The b ind ing s i t e s o f MeHg' t o 8-aza-adenine [(18, X=N, H-AAd] have a lso

been investigated: j7 a t Ng i n [(MeHg)(H-AAd)]N03 and i n [(MeHg)(AAd)].4H20 t

a t N3, Ng i n [(MeHg),(AAd)lNO,.H,O and a t N1, N6, Ng i n [(MeHg)3(AAd-H)]N03. Binding o f MeHg' t o the guanine bases o f the dinucleotides, c y t i d y l y l ( 3 ' - 5 ' ) - guanosine and the deoxy analogue, occurs p r e f e r e n t i a l l y a t N7 as determined from 1 3 C n.m.r. spectroscopy. 3 8 The MeHg' complexes o f the sulphur-containing nucleosides, 6-HS- and 2-H2N-6-%-purine r i bosi de, have been prepared i n aqueous so lut ion. Complexes conta in ing b ind ing t o S, t o S,N and S,N,C were i d e n t i f i e d from n.m.r. spectral data. 3 9 4-Methylpyrimidine-2-thione reacts w i t h MeHgOH t o give the Hg-S bonded," MeHg(SC6H2N2Me-2) (19); the X-ray s t ruc tu re o f (19) consis ts o f a p a i r of molecules w i t h a Hg ... Hg distance o f on ly 3.10 w. (Hg-S 2.437(8) f l ) . Mercury-sulphur bonding was a lso found i n the s o l i d complex o f 2 - H S - ~ y r i d i n e ~ ~ , [bteHgSC5H4N-g] [Hg-S 2.374(2) R; 8: MeHg-S2C(0)Me[Hg-S, 2.396(6), Hg.. .S2 3.201(6) 8, Formation constants have been determined from n .m.r. data f o r t h i a crown-ether complexes43 w i t h MeHgOCOCF3 i n CH2C12 and f o r MeHg' complexes w i t h various Se

conta in ing compounds, i nc l uding . sel eno-acids , HSe ( CH2)nC02H, and selenocysteine,"" i n aqueous s o l u t i o n . 4 4 The formation constants f o r the selenium complexes are up to 10 times la rger than the corresponding sulphur ones.

Pb o r -Sn compounds w i t h Hg". MeHgOH i n water have been determined by a la rge angle X-ray sca t te r ing technique!6

the two ca t ion ic u n i t s are l i n k e d via

Hg.. .N ( in t ramolecular ) 2.98(5)

i.r. and 13C n.m.r. data p o i n t to Hg ... N i n so lu t ion ] and42 i n monomeric CHgS, 176.1(7)"].

Methylmercury(+) can be generated45 i n sea-water from i n t e r a c t i o n o f methyl- Structures o f solvated MeHgX i n pyr id ine and

5:4 Other a l k y l der ivat ives. from H s ( O ~ C C F ~ ) ~ , ( i i ) RSCH2HgC1, from Bu3SnCH2SPh and HgC12, ( i i i ) BrCH2HgX (X=Br o r ON02), from HgBr2 and CH2N2 i n Et20 ( i . r . and Raman spectra reported)." and ( i v ) Hg[CH(EPh2)212 (20) from4' (Ph2P)2CHLi and HgC12. (20) i s C. Reaction4' o f HC(PPh3)3 w i t h H ~ ( O A C ) ~ provided HC[PPHh2Hg(0Ac)213 as shown by 31P and"'Hg n.m.r. data.

The c rys ta l s t ructures o f the tr imercurated ace t ic ac id der ivat ives, [Hg (H20Hg) ( ON02Hg)CC02]N03 (21 ) and [ ( 02NOHg)3CC02H]. 1HN03 ( 2 2 ) have been determined. through C-Hg-0 connections; i n contrast, ( 2 2 ) e x i s t s as d isc re te molecules.50

Syntheses have been reported f o r ( i ) (CF3)2Hg,

Binding o f Hg t o

The ca t ion o f (21) consists o f i n f i n i t e chains o f monomers l i n k e d


I n B-diketone complexes, [RC(O)CR'C(O)Rl HgX, mercury i s bound t o carbon, even i f s t e r i c a l l y hindered, o r i f one 0 has been rep laced by NR . analogues, b ind ing i s a t S, as shown51 i n [ButC(0)C=CButS],Hg.

2 However f o r t h i a

5.5 Aryl d e r i va ti ves , The compound, (2 ,5-Br2-4-MeOC6H4)2Hg, has been produced by the p y r o l y s i s a t 190-220°C o f ( 2,5-Br2-4-MeOC6H2C02)2Hg; no

mercurated a r y l d e r i v a t i v e w!s p r o d ~ c e d . ~ ' 199Hg-'99Hg sp in-sp in coup l i ng constants have been measured5 f o r t he u n s y m e t r i c dimercurated arenes, 3-Me-4-HO-5,6-(HgX)2C6HCH0 (X=02CCF3, B r o r C1 ), 2-02N-4,6-(CF3C02Hg)2C6H20R

(R=H o r Me) and 4-Me0-2,5-(CF3C02Hg)2C6H2C02H. are a v a i l a b l e d i r e c t l y f rom arenes and Hg(02CCF3)2 i n CF3C02H.

s t ruc tu res have been determined f o r ( i ) 3 3 ~ , ~ , ~ - ( B U ~ C H ~ ) ~ C ~ H ~ H ~ O ~ C C F ~ , ( i i ) 5 4

- 0-Eto2CC6H4HgC1 (Hg.. .O 2.734 8 ) , ( i i i ) ~ - ( M ~ c o s ~ ) ~ c ~ H ~ (23) [xanthates a r e m ~ n o d e n t a t e ] ~ ~ and ( i v ) [(PhHg)20H]BF4.H20 [(Hg-O-Hg 126"; Hg ... Hg 3.639 8 ) ) : 6 lg9Hg values i n d i c a t e t h a t the s o l i d s t a t e s t r u c t u r e i s mainta ined i n

so lu t i on . 56

These dimercurated arenes Crysta l

Cleavage" o f phenylene- and polyphenyl ene-mercurials by HgX2 produce 0- (XHg)2C6Y4 ( Y d , c1 o r F), (2-XHgC6H4), O r ~-XHgC6H4C6H4HgX-~ .

5.6 Oxymercuration. Ni t r a t o m e r c u r a t i ~ n ~ ~ [us ing Hg(N03)3 i n CH2C12] and

sulphonylmercuration (us ing p-MeC6H4SO2Na, HgCl i n H20-CH2C1 *) have been

reported." produced stereoisomers o f 2,8-(XHgCH2)2-1 ,7-dioxaspiro [5.5]undecane, separable by v.P.c.; 'H,13C and lg9Hg n.m.r. spect ra were obta ined.60

occurred us ing Hg(OAc)2, ButOOH ( 2 equiv.) and 20 mol % HCW4; a f t e r t reatment

w i t h Br-, BrHgCH2CH2CRR'OOBut were i so la ted . 6 1

heptane w i t h Hg(OR)2 i n CH2C12 gave trans-3-RO-~-C1HgCH2-cyclohexanol. 6 2

The a d d i t i o n o f Hg(OAc)2 t o R ' C X R ' , i n CH3C02H prov ide ace toxyv iny l - mercu r ia l s i n o v e r a l l 2nd o rde r processes.

Oxymercuration o f [CH2=CH(CH2)312C0, w i t h Hg(OAc)2 i n aqueous THF

tert-Butylperoxymercuration o f 1 ,l-R,R'-cyclopropane (R,R'=H, a1 k y l o r a r y l )

Treatment o f 3-HO-bicyclo [4.1 .Ol

The r e a c t i v e r a t e i s decreased by e l e c t r o n wi thdrawing groups.

5.7 A1 kyny l compounds. RCXHgSiMe3; 1r.m.r. spect ra have been repor ted. 6 4 Compounds, PhHgCXSF5 and

(F5SC'-C)Hg, have been generated f rom HECSF5; "F, n.m.r. and m.s. data have been presented .

Exchange reac t i ons o f (RC'-C)2Hg and (Me3Si)2Hg produce

5.8 Miscel laneous react ions.

mercu r ia l s us ing CF30F o r CH3C02F.

RCECR' (to g i v e RButC=CR'HgC1), w i t h CH2=CHY [Y=(Et0)2P0, PhS02, 2 -o2~C6H4 o r

Formation66 o f ArF has been achieved from a r y l - Free r a d i c a l . react ions o f organomercurials

t ( i ) the photo-s t imulated f r e e r a d i c a l reac t i ons o f Bu HgCl writh

Group ZZ: The Alkaline Earths and Zinc and its Congeners 21

Ph3Si ] to g i v e ButCH2CHYHgC1, and w i t h Ar2C=CH2 and (ii) r e a c t i o n s o f PhCXY (Y=PhS02, I , PhS, Bu3Sn, PhCXHg) w i t h RHgX, which y i e l d s PhCXR.

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T. Amano, T. Ota, K. Yoshikawa, T. Sana, Y. Ohuchi, F. Sato, M. Shiono, and Y , F u j i t a , Bul l . Chem. SOC. Jpn., 1986, 2, 1656. Catalysed hydromagnesiation of p-Me2C=CHCH2C6H4CHMeC02H. A.G. Schul tz , L. Flood,and J . D . Springer , J. Org. Chem., 1986, 51, 838. Addition of RMgX t o py r id ine r ings .

N. Furukawa, T. Shibutani , K. Matsumura, and H. Fu j iha ra , Tetrahedron L e t t . , 1986, 27, 3899. Pyridyl- and quinolyl-MgXCRMgX from PhMgBr and PSOPh.

R.A. Kjonaas and E . J . V a w t e r , J. Org. Chem., 1986, 51, 3997. 1,4-Addition of RMgX t o a,B-unsaturated ketones, mediated by ZnC12.TMED.

A.M. Caporusso, L. La rd icc i , and F. d Settimo, Gazz. Chim. I ta l . , 1986, 116, 599. f Reactions of R2C=C=CHBr and Bu 2M (M=Mg o r Zn) . D. J. Milner, 3 . Organomet. Chem., 1986, 302, 147. and RMgX.

E-RC~F~CN from p-(NC)*C6F4

B. Miller and J.G5. Haggerty, J. O r . Chem., 1986, 51, 174. S.e . t . i n r e a c t i o n s of 2-quinol a c e t a t e s w i th Pri-Mg c:mpounds.

C.G. S c r e t t a s and B.R. S t e e l e , J. Organomet. Chem., 1986, 317, 137. Ketones from R' CHO and unsolvated Bu2Mg i n hydrocarbons.

B. Rei ts toen, L. K i l aas , and T. Anthonsen, Acta Chem. Scand., P a r t B, 1986, 40, 441. Inve r t ed s t e r e o s e l e c t i v i t y i n a d d i t i o n of RMgX t o c h i r a l aldehydes, i n presence of polye the r s .

Zinc.

P. Knochel and J.F. Normant, J. Organomet. Chem., 1986, 2, 1. Allylic-Zn bromides and R C X H .

R.W. Lang, Helv. Chim. Acta, 1986, 69, 881.

1.1. Latkin and V.V. Fo t in , J. O r . Chem. USSR, 1986, 22, 659. RR'CZnBrC02R2 and R3XCHC12 (X=O 0: S ) .

Cadmium

Yu.A. Aleksandrov, S.A. Lebedev and N.V. Kuznetsova, Zh. Obshch. Khim., 1986, - 56, 969.

L. Bo and A.G. F a l l i s , Tetrahedron L e t t . , 1986, 27, 5193. Reaction of a l l y l - Cd wi th aldehydes.

-

CF CC12ZnC1 and CHzO. 3

Decomposition of MeZCd.

3 Boron with the Exception of the Carbaboranes

BY J. W. WILSON

1 I n t r o d u c t i o n

Following t h e p r a c t i c e o f r e c e n t y e a r s t h i s c h a p t e r is an a t t empt t o g i v e a balanced r e p o r t on t h e s i g n i f i c a n t chemistry o f organoboron compounds c o n t a i n i n g a t l e a s t one boron-carbon bond. I t is no t t h e r e f o r e a comprehensive review of t h e chemistry o f o r g a n i c compounds of boron.

2 Books and Reviews

An information source-book on o r g a n o m e t a l l i c compounds o f boron based on t h e pr imary l i t e r a t u r e up t o mid 1983 has been pub l i shed . Reviews o f t h e l i t e r a t u r e concerned wi th t h e use o f bo ranes i n o r g a n i c s y n t h e s i s (work pub l i shed i n 1983),2 t h e u s e of complexes o f d ibo rane and organoboranes on a l a b o r a t o r y and i n d u s t r i a l s c a l e 3 and a comprehensive overview o f s e l e c t i v e hydrobora t ion and t h e s y n t h e t i c u t i l i t y of t h e organoboranes so o b t a i n e d 4 have appeared. More s p e c i f i c a l l y , t h e r e have been t w o accoun t s o f i s o t o p e i n c o r p o r a t i o n u s i n g o r g a n ~ b o r a n e s ~ J

metal complexes. and a r e p o r t on borabenzene

I t shou ld be n o t e d h e r e t h a t an e f f o r t i's b e i n g made t o p u b l i s h t h e f u l l d e t a i l s o f much of t h e chemistry t h a t has emanated from H . C. Brown's group i n t h e form o f communications and reviews.*

3 Uses o f Organoboron Compounds i n S y n t h e s i s

Experimental and t h e o r e t i c a l i n v e s t i g a t i o n s i n t o t h e hydroborat ion of a lkenes u s i n g 9-BBN have p rov ided a d d i t i o n a l ev idence s u p p o r t i n g an e a r l y t r a n s i t i o n s ta te which h a s r e t e n t i o n of a l k e n e c h a r a c t e r . g Methyl and dimethylborane can be r e a d i l y l i b e r a t e d from t h e e a s i l y p repa red bo rohydr ides . They show e x c e l l e n t r e g i o s e l e c t i v i t y i n t h e hydroborat ion o f a lkenes g i v i n g a lky lme thy lboranes which can be conve r t ed t o t h e co r re spond ing t e r t i a r y a l c o h o l s i n h igh y i e l d s . 1 ° A d e t a i l e d s t u d y has been made o f t h e hydrobora t ion o f c y c l i c d i e n e s wi th r e p r e s e n t a t i v e r e a g e n t s and h a s shown t h a t h igh y i e l d s of monohydroborated p roduc t s are o b t a i n e d w i t h six-membered d i e n e systems. As r i n g s i z e i n c r e a s e s , however , t h e p r o p o r t i o n o f t h i s


Boron with the Exception of the Carbaboranes 25

produc t d i m i n i s h e s and t h a t of t h e d ihydrobora t ed p roduc t i n c r e a s e s . The monohydroborated p r o d u c t s ( a l l y l b o r a n e s ) are r e a d i l y d e r i v a t i s e d t o t h e co r re spond ing e t h a n o l s , Comparison of. t h e r e d u c i n g characteristics of d i b o r a n e , t hexy lborane and thexy lch lo roborane have been made and t h e r e a c t i o n s of t h e l a s t r e a g e n t , as its d ime thy l su lph ide complex i n d i ch lo romethane , w i th f i f t y - s i x s e l e c t e d o r g a n i c compounds c o n t a i n i n g r e p r e s e n t a t i v e f u n c t i o n a l groups i n v e s t i g a t e d . 1 2 The same r e a g e n t h a s been used i n t h e g e n e r a l s t e r e o s e l e c t i v e s y n t h e s i s o f (E) -d i subs t i t u t e d a l k e n e s t o make pheromones c o n t a i n i n g t h i s moiety. Thexylborane has been used t o h y d r o b o r a t e chiral cyclohexene-derived a l l y l i c a l c o h o l s and whereas isomeric 2 -e thy l i dene cyc lohexano l s show poor stereo- s e l e c t i v i t y , 1-(1 '-hydroxyalby1)cyclohexenes show up t o 50:l d i s c r i m i n a t i o n . 1 4 The hydrobora t ion o f r e p r e s e n t a t i v e h e t e r o c y c l i c compounds b e a r i n g a v i n y l or propenyl s u b s t i t u e n t w i th a v a r i e t y o f r e a g e n t s h a s been i n v e s t i g a t e d s y s t e m a t i c a l l y i n an a t t e m p t t o es tab l i sh d i r e c t i v e e f f e c t s 1 5 and N-alkylpropargylphosphoramides are hydrobora t ed w i t h p r e f e r e n t i a l fo rma t ion o f y-boron d e r i v a t i v e s (90-100%) and e x c e l l e n t s t e r e o s p e c i f i c i t y (loo%, z). l 6 development o f a g e n e r a l s t e r e o s p e c i f i c s y n t h e s i s , u t i l i s i n g a v a r i e t y o f h y d r o b o r a t i n g a g e n t s , of ( E ) - d i s u b s t i t u t e d a l k e n e s and t h e i r conve r s ion i n t o t h e co r re spond ing ke tones i n e x c e l l e n t y i e l d s has been r e p o r t e d . 1 7 Organoboranes c a t a l y s e t h e h i g h l y e f f i c i e n t r e g i o and chemose lec t ive hydroaluminat ion o f monosubs t i t u t ed a l k e n e s l * and selected d i a l k y l h a l o b o r a n e s r educe benzaldehyde a t a rate tha t is much faster t h a n related t r i a l k y l b o r a n e s . l 9 A mechanism is proposed t h a t can account f o r these major d i f f e r e n c e s . The d i r e c t and s e l e c t i v e s y n t h e s i s o f (Z,Z)-l-bromo-l,3-dienes and (,E, z)-1 , 3-dienes by a hydroboration-bromoboration sequence h a s been r e p o r t e d . 2 0 compare w e l l w i t h t h e best r e a g e n t s a v a i l a b l e f o r t h e s t e r e o and chemose lec t ive r e d u c t i o n of ca rbony l compounds and i t is claimed t o p o s s e s s advan tages o v e r o t h e r r e a g e n t s i n terms o f t h e work up p r o c e d u r e s r e q u i r e d . 2 1

Asymmetric r educ ing a g e n t s based on ch i r a l 9-alkoxy-9-BBN

The

Po tas s ium t r i p h e n y l b o r o h y d r i d e h a s p r o p e r t i e s t h a t

d e r i v a t i v e s have been developed and t h e i r a b i l i t y t o r educe acetophenone and 3-methyl-2-butanone assessed.22 Furthermore t h e new ch i r a l r e a g e n t , po ta s s ium 9-0-(1,2:5,6-di-O-isopropylidene-a-D- -glucofuranosyl)-9-BBNH reduces a-keto esters t o t h e co r re spond ing a-hydroxy esters w i t h o p t i c a l p u r i t i e s approach ing 100% ee.* In a d d i t i o n a r e a g e n t , based on (R,R_) or (S,S_)-2,5-dimethylborolane,


f o r t h e v e r y e f f i c i e n t asymmetric r e d u c t i o n o f a v a r i e t y of p r o c h i r a l d i a l k y l k e t o n e s h a s been r e p o r t e d 2 4 and a mechanism foy t h e r e a c t i o n proposed. 2 5 The same research group has a l s o produced a r eagen t f o r asymmetr ic aldol r e a c t i o n s which is a n t i - s e l e c t i v e and c o n s i s t e n t l y a c h i e v e s an e n a n t i o s e l e c t i v i t y greater than 80:1.26 p u r i t y have been p repa red from r e a d i l y a v a i l a b l e p r o c h i r a l o l e f i n s and monoisopinocampheylborane ( IpcBH2 ) and a r e conve r t ed stereo- s p e c i f i c a l l y v i a a t w o s t a g e s y n t h e s i s i n t o t h e co r re spond ing (+)

o r ( - ) primary Mat t e son ' s d i r e c t e d asymmetric s y n t h e s i s t echn ique based on chiral b o r o n i c esters has been shown t o be compatible w i t h v a r i o u s f u n c t i o n a l groups. I ts promise h a s been demonstrated by t h e s y n t h e s i s of a c h i r a l v i c - d i o l , an alcohol having three a d j a c e n t c h i r a l c e n t r e s , a chiral a , y - d i o l , a c h i r a l vic-amino a l c o h o l and three i n s e c t pheromones each c o n t a i n i n g two c h i r a l c e n t r e s . 2 8 (S,S_)-diisopropylethanediol which can then be used i t s e l f as an e f f e c t i v e ( R ) d i r e c t i n g group i n t h e g e n e r a l s y n t h e s i s . 2 9 An a l t e r n a t i v e t o t h i s g e n e r a l s y n t h e s i s , based upon t h e a l l y 1 rearrangement , h a s been used t o make o p t i c a l l y a c t i v e a-chloro-(E)- - c r o t y l b o r o n a t e esters which p rove t o be h i g h l y e n a n t i o s e l e c t i v e . a - C h l o r o a l l y l b o r o n a t e s of 92% ae. add t o a c h i r a l a ldehydes t o y i e l d a l l y l i c a l c o h o l s o f 82-928 e.e.3' whereas s t u d i e s on t h e s t e r e o - chemis t ry o f t h e p r o d u c t s from t h e r e a c t i o n between s u b s t i t u t e d a l l y l b o r o n a t e s and c h i r a l a ldehydes has thrown some l i g h t on f a c t o r s i n f l u e n c i n g aldehyde d i a s t e r e o f a c i a l s e l e c t i v i t y . 32 a c i d reacts wi th 6-hydroxyketones t o g i v e t h e threo-diols w i t h

unprecedented l e v e l s of 1,3-asymmetr ic i n d u c t i o n . 3 3

2-Alkyl-1,3,2-dioxaborinanes o f e s s e n t i a l l y 100% o p t i c a l

The method has a l s o been used t o p r e p a r e

-

A l l e n y l b o r o n i c

The u s e of b o r o n i c and b o r i n i c esters i n c h i r a l s y n t h e s e s w i l l be encouraged by a simple p rocedure f o r upgrad ing t h e opt ical p u r i t y o f such compounds t o l e v e l s approach ing

as r e a g e n t s f o r e n a n t i o s e l e c t i v e processes. S t u d i e s o n t h e secondary k i n e t i c i s o t o p e effect o f deu te r ium on e n a n t i o s e l e c t i v e hydrobora t ions w i t h ( + ) ( I ~ c ) ~ B H have p rov ided s i g n i f i c a n t e x p e r i m e n t a l e v i d e n c e which p r o v i d e s a t es t f o r any de ta i led

e x p l a n a t i o n o f t h e p r o c e s s . 3 5 s y s t e m a t i c s t u d y w i t h r e p r e s e n t a t i v e h e t e r o c y c l e s b e a r i n g an e n d o c y c l i c double bond i n o r d e r t o es tab l i sh t h e asymmetric i n d u c t i o n ach ieved . I t t u r n s o u t t h a t the r e a c t i o n p r o v i d e s a s i m p l e and e f f i c i e n t method of s y n t h e s i s i n g h e t e r o c y c l i c b o r o n a t e s

Diisopinocampheylborane d e r i v a t i v e s c o n t i n u e t o be a t t r a c t i v e

The r eagen t has been used i n a


and both enan t iomers o f c h i r a l h e t e r o c y c l i c a l e ~ h o l s . ~ ~

B ( 1 p ~ ) ~ h a s been used t o e s t a b l i s h t h e mig ra to ry a p t i t u d e of t h e isopinocampheyl group and t o demons t r a t e t h a t t h e i o d i n e induced rearrangement o f l i t h i u m a l k y n y l t r i a l k y l b o r a t e s 'is h i g h l y stereo- s p e c i f i c and p roceeds w i t h e s s e n t i a l l y complete r e t e n t i o n o f c o n f i g u r a t i o n at t h e m i g r a t i n g c e n t r e . 37 a l k y l k e t o n e s wi th ( - ) ( 1 p ~ ) ~ B C l p roceeds wi th similar h i g h e n a n t i o m e r i c e x c e s s t o t h a t shown by other s y s t e m s . 3 B ( I p ~ ) ~ B o " f / P r l ~ N E t leads t o =-adducts i n good e n a n t i o m e r i c e x c e s s e s (66-90%) w i t h high d i a s t e r e o s e l e c t i v i t y i n t h e aldol condensa t ion between d i e t h y l k e t o n e s and s i m p l e a ldehydes . C h i r a l d i a l k y l b o r a n e t r i f l a t e r e a g e n t s are n o t as e f f e c t i v e . 39 ( 1 p ~ ) ~ B adds smoothly t o a ldehydes w i t h remarkable e n a n t i o - s e l e c t i v i t y . The r e a c t i o n is tempera tu re dependent and less f a v o u r a b l e w i t h k e t o n e s . I t h a s also been d i s c o v e r e d t h a t t h e a l l y l b o r a t i o n of aldehydes is q u i t e g e n e r a l and n o t dependent on t h e n a t u r e o f t h e aldehyde. 4 0

first example of t h e r e g i o and s t e r e o s e l e c t i v e p r e p a r a t i o n of o p t i c a l l y p u r e ( g ) and (5) c r o t y l b o r a n e s which have been used t o produce a l l four s t e r e o i s o m e r s o f 6-methylhomoallyl a l c o h o l s from ace ta ldehyde and t h e s t u d i e s ex tended t o a range o f r e p r e s e n t a t i v e aldehydes. D i i s o p r o p y l tar t ra te modi f i ed ( E ) - c r o t y l b o r o n a t e h a s also been shown t o b e a h i g h l y e n a n t i o s e l e c t i v e r e a g e n t . 4 2

Sec -bu ty l

Reduct ion o f a - t e r t i a r y

The r e a g e n t

A l ly l -

The ( 1 p ~ ) ~ B group h a s f e a t u r e d i n t h e

A nove l pho tochemica l ly induced m i g r a t i o n o f an a l k y l group

Furthermore t r i a l k y l b o r a n e s r e a d i l y a l k y l a t e f rom boron t o carbon i n dialkylborylacetylacetonate complexes has been d i s ~ o v e r e d . ~ ~ a-hydroxy a r y l a ldehydes and a- formy l k e t o n e s v i a d i a l k y l b o r y 1

complexes. B- trans-1-alkenyl-9-BBN undergoes f a c i l e react i o n w i t h a-halo c a r b a n i o n s p r o v i d i n g t h e co r re spond ing 8 , y-unsa tu ra t ed esters, k e t o n e s o r n i t r i l e s i n good y i e l d s 4 5 and t h e a l k y l a t i o n of a boron s t a b i l i s e d ca rban ion c o n t a i n i n g an a -pheny l th io group takes p l a c e on s u l p h u r r a t h e r t han carbon. T h i s is t h e first t i m e such an e l e c t r o p h i l i c a t t a c k a t a hetero-atom a l p h a t o a ca rban ion rather t h a n t h e carbon atom c e n t r e o f t h e ca rban ion h a s been d e f i n e d . 4 6 The i n t e r e s t i n me ta l c a t a l y s e d r e a c t i o n s c o n t i n u e s . P a l l a d i u m c a t a l y s e d c ross -coup l ing react i o n s of B-alkyl-9-BBN o r t r i a l k y l b o r a n e s w i t h a r y l and 1 -a lkeny l h a l i d e s takes p l a c e r e a d i l y t o y i e l d a l k y l a t e d a r e n e s or a l k e n e s i n e x c e l l e n t y i e l d s 4 7 whereas (2 ) -1 -a lkeny lborona te s w i t h 1-bromoalkenes or a r y l i o d i d e s g i v e con juga ted (l3,Z) o r (g,z) a l k a d i e n e s o r arylated (2-)-alkenes. 48

Carbonylat i v e c ros s -coup l ing o f organoboranes w i t h a r y l i o d i d e s o r

28 Organomtalk ChemiMry

benzy l h a l i d e s c a t a l y s e d by t h e same e l emen t i n t h e p resence o f Zn( a c a c ) ~ g i v e s unsymmetr ical k e t o n e s i n r e a s o n a b l e y i e l d s . 49 Symmetrical ( l3 ,g)- l ,3-dienes are produced q u a n t i t a t i v e l y by a z i n c promoted r e d u c t i v e c o u p l i n g r e a c t i o n i n v o l v i n g (E)-1-alkenyl d i a l k y l methoxy borates.50 Cuprous iodide c a t a l y s e d c ross -coup l ing r e a c t i o n s i n v o l v i n g tr i m e t h y l s i l y l s u b s t i t u t e d organoboron d e r i v a t i v e s l e a d s t o t h e stereoselect i v e s y n t h e s i s o f a l l y 1 and a lkyny l s u b s t i t u t e d ( g ) - v i n y l s i l a n e s . 5 1

have been developed for the r a p i d p r o t o n o l y s i s o f r e p r e s e n t a t i v e a l k e n y l d i a l k y l b o r a n e s which p r o v i d e s a s i m p l i f i e d , s t e r e o s p e c i f i c s y n t h e s i s of (5 ) - a lkenes . 5 2

Details and u s e s of t h e t r a n s f e r r e a c t i o n i n v o l v i n g 1-alkynyltrialkylborates v i a i o d o n a t i o n have been p u b l i s h e d . r e a c t i o n takes p l a c e a t low t e m p e r a t u r e t o g i v e s u b s t i t u t e d a lkynes and t h e method is a p p l i c a b l e t o p r imary , s econda ry , a romat i c and f u n c t i o n a l l y s u b s t i t u t e d g roups and can be ex tended t o t e r m i n a l a lkynes . A sequence f o r t h e s y n t h e s i s o f unsymmetrical a lkynes has been developed and t h e e f f e c t of s e v e r a l p o t e n t i a l b l o c k i n g groups examined i n order to a c h i e v e s e l e c t i v e mig ra t ion and hence i n c r e a s e t h e e f f i c i e n c y of t h e m e t h 0 d . 5 ~

t echn ique has been u s e d t o p r e p a r e v a r i o u s i n s e c t pheromones c o n t a i n i n g s t r a i g h t cha in (Z)-mono-olef inic s t r u c t u r e s , 54 react ion o f 1- a l k y n y l l i t h iums w i t h B-met hoxybor inane and B-methylboracyclanes h a s been r e f i n e d i n t o a g e n e r a l one-pot s y n t h e s i s of 6 and 7-alkyn-1-01s v i a t h e iodona t ion p rocedure . (2)-(1-Substituted-1-alkeny1)boronic esters can be p r e p a r e d i n a h i g h l y r e g i o and s t e r e o s e l e c t i v e manner and e i t h e r isolated i n t h e p u r e form o r o x i d i s e d d i r e c t l y t o t h e co r re spond ing k e t o n e . 5 6 Simple and v e r s a t i l e direct r o u t e s t o ( z ) - a , B-unsaturated k e t o n e s , s p e c i f i c a l l y p r o t e c t e d 1,3 d i k e t o n e s and o t h e r k e t o n i c s p e c i e s s t a r t i n g from a l k y n y l t r i a l k y l borates have been d i s c o v e r e d . The addi t i on o f su lphen imines t o a l l y l b o r o n a t e s g i v e s homoallyl- su lphen imides i n a s l u g g i s h b u t e f f i c i e n t r e a c t i o n . 5 *

Extremely mi ld , e s s e n t i a l l y n e u t r a l c o n d i t i o n s u s i n g methanol

The

The

The

4 P r e p a r a t i o n s and Reac t ions o f Organoboron Compounds

Convenient p rocedures f o r t h e g e n e r a t i o n of bo rane , mono and d i a l k y l b o r a n e s f r o m l i t h i u m borohydr ide have been r e p o r t e d s 9 and a h i g h l y e f f i c i e n t s y n t h e s i s of t r i o r g a n y l b o r a n e s v i a a mod i f i ed s t a n d a r d o r g a n o m e t a l l i c r o u t e developed. T h i s last p rocedure i n v o l v e s direct react ion of magnesium, o r g a n i c h a l i d e and


B F 3 0 e t h e r a t e i n d i e t h y l e t h e r . 6 0 then t h e r e a c t i o n r e s u l t s i n q u a n t i t a t i v e formation o f t h e tetra- o rganobora t e i n t h e one case s t u d i e d . 6 1 i n 90% y i e l d by a one-pot s y n t h e s i s i n v o l v i n g t r i e t h y l a l u m i n i u m . 62 A s t e r e o s p e c i f i c s y n t h e s i s o f B-(Z)-l-alkenyl-g-BBN d e r i v a t i v e s t h a t are n o t a v a i l a b l e by hydrobora t ion r e a c t i o n s h a s been developed.63 The 9-BBN dimer has f e a t u r e d i n thermal i s o m e r i z a t i o n and t h e r m o l y s i s s t u d i e d 4 and s imi la r s t u d i e s on dimesi tyl-3-hexyl- borane show t h a t , i n comparison to t h e diphenyl compound, it is q u i t e r e s i s t a n t t o thermal i s o m e r i z a t i o n and an e x p l a n a t i o n is o f f e r e d .

t r ime thy lamine N-oxide66 and o x i d a t i o n o f a c h i r a l b o r o n i c a c i d by flavoenzyme cyclohexanone oxygenase p roceeds wi th r e t e n t i o n o f c o n f i g u r a t i o n at t h e m i g r a t i n g c e n t r e i n an analogous manner t o pe rox ide o x i d a t i o n . 6 7 One e l e c t r o n o x i d a t i o n o f a l k y l t r i p h e n y l borate a n i o n s leads t o carbon-boron bond c l eavage and t h e

formation o f free a l k y l radicals. *

manner69 and t h e r e a c t i o n o f c y c l i c b o r o n i c e s t e r s p o s s e s s i n g a wide v a r i e t y o f s teric requ i r emen t s w i t h potassium hydr ide g i v e s rise t o t h e co r re spond ing bo rohydr ides . These r e p r e s e n t a new class o f r educ ing a g e n t s whose s t a b i l i t y and r e a c t i v i t y have been exp lo red . 70 Copper( I ) a lky lborohydr ides are o b t a i n e d from 1 :1 mix tu res of cuprous c h l o r i d e and sodium borohydride on r e a c t i o n wi th a lkenes i n THF.71

New methods for t h e s y n t h e s i s of p rox ima l ly f u n c t i o n a l i s e d a r y l b o r a n e s and s i l a n e s have been developed72 and their a b i l i t y t o complex f l u o r i d e i o n s i n v e s t i g a t e d . 73

Two groups have r e p o r t e d examples o f 1 , 3 - d i b o r e t a n e d i i d e an ions (1). In t h e first s t u d y t h e c r y s t a l s t r u c t u r e o f a l i t h i u m d e r i v a t i v e shows t h a t i n t h e s o l i d s t a t e t h e system is dimeric i n t h e form of a sandwich w i t h a " f i l l i n g " of a f o u r l i t h i u m atom l a y e r 7 4 whereas p r o t o n a t i o n o r r e a c t i o n w i t h PhPAuCl o f a second d ian ion y i e l d s a puckered o r p l a n a r 1 , 3 d i b o r e t a n e r e s p e c t i v e l y . 75 The l i t h i u m s a l t o f l , 2 -d ibo ra t abenzene ( 2 ) has been i s o l a t e d , i ts c r y s t a l s t r u c t u r e determined and t h e u s e o f t h e anion as a l i g a n d i n rhodium and ruthenium complexes exp lo red .76 Pen ta -a ry l b o r o l e chemistry can be e x p l a i n e d s t r a i g h t f o r w a r d l y i n terms of t h e a n t i a r o m a t i c c h a r a c t e r o f t h e 4n e l e c t r o n r i n g . 77 The p r o p e r t i e s of C-unsubs t i t u t ed 2 and 3-borolenes have been r e p o r t e d t o g e t h e r

I f t h e s o l v e n t is changed t o THF

T r i e t h y l b o r a n e can be made

S e q u e n t i a l o x i d a t i o n of t r i a l k y l b o r a n e s takes p l a c e w i t h

Potassium t r i s i a m y l b o r o h y d r i d e can now be made i n a conven ien t


R ' R'

( 2 )

x x \ / AL

R,B- 0: :O-BR, A l I \

x x ( 3 )

But I N

R-6, / \ ,6-R

N

I 0 Ut


w i t h some boratacyclopentene s a l t s . 7 8

Aminomethyleneborane precursors have been s tudied79 and evidence f o r such a s p e c i e s obta ined from thermal decomposition s t u d i e s . 8 0 Boron func t iona l ized diborylamines have been synthes isede l as has (2,6-diisopropylphenylimino)thexyl borane which can be s t o r e d f o r prolonged per iods .82 c h a r a c t e r i z a t i o n and prel iminary i n v e s t i g a t i o n s of t h e chemistry of Me3N*BH2CRRrCN systems, a new class of m i n e boranes, has been reported8 have been made. 8 4

Two improved procedures f o r t h e prepara t ion of b o r l a i c and boronic esters from "ate" complexes have been developeda5 and a p r a c t i c a l s y n t h e s i s of dichloromethyl and 1 , l - d i c h l o r o e t h y l boronic esters repor ted .86 homologating agents f o r t r i a l k y l b o r a n e s , b o r i n i c and boronic esters have been explored and LiCHC12, LiCHClSIMe3 and LiCH(0Me)SPh shown t o work w e l l with a l l t h r e e s u b s t r a t e s . Other reagents a r e e f f e c t i v e w i t h t r i a l k y l b o r a n e s b u t no t with boronic esters.87 Avai lable procedures f o r homologation of boronic esters have been c r i t i c a l l y examined and a more convenient r o u t e r e p o r t e d . 8 8 r 8 g The la rge-sca le s y n t h e s i s of pinacol iodomethaneboronate and its a p p l i c a t i o n t o the s y n t h e s i s of ( acy1amino)methane boronic esters has been inves t iga ted . A series of N-substituted-2-carboxamido- -phenylboronic a c i d anhydrides have been madeg1 and phenylboronic a c i d i t s e l f used t o mediate i n t h e "uphi l l " t r a n s p o r t of mono- sacchar ides across an organic l i q u i d membrane.92 dimeric( dihalogenoa1uminiooxy)diorganoboranes ( 3 ) , which are d e r i v a t i v e s of t h e corresponding b o r i n i c a c i d , have been c h a r a c t e r i s e d and a c r y s t a l s t r u c t u r e repor ted .

Several accounts of t h e s y n t h e s i s and s t r u c t u r e s of systems conta in ing boron i n h e t e r o c y c l i c molecules have appeared. Novel organoboron-oxy-aluminium h a l i d e s have been made of which (4) is t y p i c a l . 9 4

organodiboroxanes and boroxins . A d e t a i l e d s tudy of t h e r e a c t i o n s of boroxins and diboroxanes with pyrazole h a s been repor ted .96 Diazabore t id ines ( 5 ) and borazines have been obta ined by t h e r e a c t i o n of RBX2 w i t h t i n precursors and t h e i r p r o p e r t i e s s tud ied .g7 A series of 2,3-dihydro-4H-lt 3,2-selenazoborin-4-ones (6 ) have been preparedg -thia-5-boracyclooctane shows it conta ins a sulphur-boron d a t i v e bond.99

The s y n t h e s i s ,

and a series of bory la ted carbodiimides ( R2B-N=C=N-BR2)

The e f f e c t i v e n e s s of r e p r e s e n t a t i v e

C r y s t a l l i n e

The same research group has a l s o synthes ised che la ted

and t h e X-ray s t r u c t u r e determinat ion of 5-chloro-1-

The same f e a t u r e is a l s o present i n a new t r i c y c l i c


E t yJR R'

Et 0

R R

0 0

( 8 )

SnMe

Me2Si

Me&@:

SnMc,

Ph Me, I

N-8-N

R I B

0' ' 0 u ( 9 )

( 1 0 )


B,N4S2Si2 system (7).loo a-aminodiacids t o g i v e e i t h e r mono o r b i c y c l i c compounds depending on r e a c t i o n c o n d i t i o n s and t h e s u b s t i t u e n t s on t h e d i a c i d . l o l

T r i e t h y l o r t r i p h e n y l b o r a n e s react w i t h

A i r -s t able boron i c molecu la r B-N bond and 2 - s u b s t i t u t e d , y i e l d s . T h e i r u s e anion : CHOH-CHO i n

b i c y c l i c esters ( 8 ) c o n t a i n i n g a s t r o n g i n t r a - have been o b t a i n e d v& i m i n o d i a c e t i c a c i d s 1 O 2 1 ,3 ,2 -d ioxaboro le s (9) s y n t h e s i s e d i n e x c e l l e n t as s y n t h e t i c e q u i v a l e n t s o f t h e g lyco la ldehyde ca rbohydra t e s y n t h e s i s has been demonstrated.

T r a n s f e r of s u b s t i t u t e d a romat i c groups from s i l i c o n t o boron is an e f f i c i e n t s y n t h e t i c pathway f o r t h e p r e p a r a t i o n o f a r y l - halogenoboranes and d i a ry lha logenoboranes w i t h d i f f e r e n t a r y l groups. l o 4

- t e r t - b u t y l ch lo roborane have been r e p o r t e d l o 5 and t h e r e a c t i o n of phosphonium y l i d e s wi th a l k y l d i c h l o r o b o r a n e s i n v e s t i g a t e d . O6

Methods f o r t h e p r e p a r a t i o n o f R2BX (R=Pri,But; X = H a l . ,OR' ,SMe,NH2, N H R ' , N R f 2 ) have been d e s c r i b e d and t h e i n f l u e n c e of the bulky g r o u p on t h e r e a c t i v i t y of t h e s e bo ranes examined.

a lkyny l d e r i v a t i v e s have l ed t o a new f u s e d h e t e r o c y c l e , l o 8 c h i r a l a lkenyl-( N-azolyl)boranes, l o 9 boron s u b s t i t u t e d s i l a and germa cyc lopen tad ienes , s 1 t w o isomeric h i g h l y s u b s t i t u t e d borolesl l 2

and 1 , 2 dihydro-l,2,5-disilaborepins ( 10) The p l a t i n a c y c l o - p e n t a d i e n e s (11) have also been made by similar methods. l4

Phenylbora-2,5-cyclohexadiene is a v e r s a t i l e l i g a n d p r e c u r s o r as shown by r e a c t i o n s w i t h ca rbony l and a l k e n y l complexes o f i r o n , cobalt and n i c k e l . Complexes c o n t a i n i n g t h e 2-boratanaphthalene l i g a n d show i t t o be hexahapto bonded v i a t h e boron c o n t a i n i n g r i n g t o i r o n , rhodium and l i t h i u m . l 1 6 The f i r s t complexes w i t h a 1 , 3 diborabenzene s k e l e t o n have been described. Dehydrogenating complexat ion o f b o r o l e n e s h a s produced s i m p l e pen tahap to b o r o l e complexes o f manganese, i r o n and c o b a l t and t r ip l e -decke r complexes o f rhodium. 1 1 8 , S e v e r a l roots have been used to make ( n6-arene) (n 5 - t h i a d i b o r o l e n e ) i r o n compounds and t h e i r r e a c t i o n s , s p e c t r o s c o p i c data and a c r y s t a l s t r u c t u r e r epor t ed .120 Nicke l and rhodium complexes c o n t a i n i n g t h e 2,3-dihydro-1, 3-diborole l i g a n d have been c h a r a c t e r i s e d l 2 l , 1 2 2 and a 1 ,2 -azaboro ly l ( n4 - l , 5 -cyc looc tad iene ) - c o b a l t complex s y n t h e s i s e d . The h inde red m o b i l i t y of t h e l i g a n d s i n t h i s compound have been examined by t empera tu re dependent n.m.r. measurements, 12 3

S u b s t i t u t i o n r e a c t i o n s of Cbis( t r i m e t h y l s i l y l ) a m i n o l -

Organoborat ion s t u d i e s o f a v a r i e t y o f s u b s t i t u t e d s t a n n y l


5 T h e o r e t i c a l , P h y s i c a l and S t r u c t u r a l S t u d i e s on Organoboron Compounds

Minimum ene rgy s t r u c t u r e s (6-31G*) have been o b t a i n e d f o r t h e C3BH, C3BH2+, C2B2H2 and C2BBeH four-membered r i n g systems124 and optimum geomet r i e s and r e l a t i v e e n e r g i e s of t h e f i v e most p r o b a b l e isomers w i t h t h e fo rmula C2BH5 c a l c u l a t e d . l Z 5

for t h e d i m e r i z a t i o n of b o r i r e n e t o 1,4-diboracyclohexa-2,5-diene and t h e more st able i somer 2,3,4,5-tetracarba-nido-hexaborane ( 6 )

have been s t u d i e d by semi -empi r i ca l and 2 i n i t i o methods.126 A v a r i a b l e t empera tu re 1 3 C n.m.r. s t u d y on alkoxy and a l k y l -

thio-piperidinophenylboranes i n d i c a t e s t h a t B-0 n bonding is some 1 2 k J mol-l greater than B-S n bond ing .127 A m u l t i n u c l e a r n .m.r . s t u d y of methylaminodiphenylborane h a s been r e p o r t e d and t h e 1 3 C

spectrum i n t e r p r e t e d d i f f e r e n t l y t o earlier s t u d i e s on similar compounds. l 2 Ion c y c l o t r o n r e sonance spec t roscopy has been used i n a comparat ive s t u d y of t h e behav iour o f a l k o x i d e and a lkox ide - - a lkano l i o n s w i t h a l k y l and alkoxyboranes i n t h e gas phase .129

P o s s i b l e pathways

S e v e r a l &-ray c r y s t a1 s t r u c t u r e s i n v o l v i n g mes i ty lbo rane d e r i v a t i v e s have been r e p o r t e d . t h e a d d i t i o n a l e l e c t r o n has a s m a l l e f f e c t o n t h e ground s t a t e s t r u c t u r e 1 3 0 w h i l s t s i g n i f i c a n t s h o r t e n i n g o f a B-C bond i n [CH2C6H2( 3,s M e 2 ) B M e s ~ 1- s u g g e s t s s u b s t a n t i a l boron y l i d e character and hence boron s t a b i l i z a t i o n o f t h e an ion . 3 1 Diphenylphosphino- d i m e s i t y l b o r a n e c o n t a i n s p l a n a r boron and pyramidal phosphorus atoms1 32 w h i l s t i n t h e co r re spond ing a n i o n PhPBMes2- bo th atoms are p l a n a r and t h e B-P bond l e n g t h is s h o r t e r s u g g e s t i n g t h e p r e s e n c e of m u l t i p l e bonding i n such a n i o n s , l 3

H e ( 1) p h o t o e l e c t r o n and n .m. r . s p e c t r o s c o p i c s t u d i e s on BR2X (R=Pri,But) i n d i c a t e t h a t t h e s e sys t ems co r re spond w e l l t o t h e

R = Me and E t Cases e x c e p t when X = N R 2 ' which d e v i a t e from a p l a n a r C2BNC2 confo rma t ion , - X-ray s t r u c t u r e s o f f i v e d ibo ry lamines and a b o r y l s i l y l a m i n e have been de te rmined and t h e obse rved conforma- t i o n s and bonding pa rame te r s d i s c u s s e d i n terms o f s te r ic e f f e c t s . 1 3 5 The p r e f e r r e d confo rma t ions of a series o f symmet r i ca l ly and unsymmetr ical ly s u b s t i t u t e d d ibo ry lamines have been r e v e a l e d by n.m.r. t o be a f u n c t i o n of t h e s u b s t i t u e n t s . 1 3 6 The p r e p a r a t i o n and s t r u c t u r e of ( t e r t - b u t y l i m i n o ) ( tris( t r i m e t h y l - s i l y 1 ) s i l y l ) b o r a n e have been reported and w h i l s t t h e molecule does n o t c o n t a i n a boron-carbon bond it is of r e l e v a n c e t o t h e s u b j e c t o f t h i s r e p o r t .

The s t r u c t u r e of 6Mes3- shows t h a t


I

2 3 4 5

6 7 8

9 10

11 12

13 14

15 16

17

18

19

20

21 22 23 24

25

26

27

28

29 30 31 32

33 34 35

36 37 38

39

Re f e rences

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-

1986, 51, 3394.


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46

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48 49

50 51 52 53

54 55 56 57 58 59

60 61 62 63 64 65 66 67 68 69 70

71 72 73 74

75

76

77 78

79 80 81 82 83

84

85 86

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Organometallice, 1986, 5, 2303. H. C.’ Brown and U. S. Racherla, J. Org. Chem., 1986, 51, 427. H. C. Brown and U. S. Racherla, Organometallice, 1986, 5, 391. Y.-T. Lin, J. Organomet. Chem., 1986, 317, 277. H. C. Brown, N. G. Bhat,and S. Rajagopalan, Organometallics, 1986, 5, 816. R. Koeeter and M. Yalpani, J. Org. Chem., 1986, 51, 3054. A. P e l t e r and A. Keating, Tetrahedron L e t t . , 1986, 27, 5037. J. A . Sodexquiet and M. R. Najaf i , J. Org. Chem., 1986, 51, 1330. J. A. Latham Jr. and C. Waleh, J. Chem. SOC., Chem. Comm., 1986, 527. J. Y. Lan and G. B. Schuster , Tetrahedron L e t t . , 1986, 27, 4261. C. A. Brown and 5. Krishnamurthy, J. Org. Chem., 1986, 5 l , 238. H. C. Brown, W. S. Park, J. S. Cha, B. T. Cho,and C. A . Brown, J. Org. Chem., 1986, 51, 337. S. A. Rao and M. Periaeamy, J. Organomet. Chem., 1986, 309, C39. H. E. Katz, Organometallice, 1986, 5, 2308. H. E. Katz, J. A m e r . Chem. SOC., 1986, 108, 7640. G. Schmidt, G. Baum, W . Massa,and A. Berndt, Angew. Chem. I n t . Ed. Engl.,

P. Hornbach, M. Hildenbrand, H . Pritzkow,and W . S ieber t , Angew. Chem. I n t . Ed. En@. , 1986, 25, 1112. G. E . Herberich, B. Heseneraand M. Hostalek, Angew. Chem. I n t . Ed. Engl., 1986, 25, 642. J. J. Eisch, J. E. Galle ,md S. Kozima, J. Amer. Chem. SOC., 1986, 108, 379. G. E. Herberich, W . Boveleth, B. Heseer, M. Hostalek, D. P. J. Koffer, A. Ohet,and D. SLShnen, Chem. B e r . , 1986, 2, 420. B. Glaser and H. Nath, Chem. B e r . , 1986, 119, 3253. B. G l a s e r and H. N‘dth, Chem. B e r . , 1986, 119, 3856. H. Nijth, P. Otto,and W. S torch, Chem. Ber., 1986, 119, 2517. M. Armbrecht and A. Meller, J. Organomet. Chem., 1986, 311, 1. J. L. P e t e r s , V. M. Norwood II1,and K . W . Morse, Inorg. Chem., 1986, 25, 3713. W. Einholz and W. Haubold, 2. Naturforsch. B: Anorg. Chem., Org. Chem., 1986, 41B, 1367. H. C. Brown, M. Srebnik,and T. E. Cole, Organornetallice, 1986, 5, 2300. D. S. Matteson and G. D. Hurst , Organometallics, 1986, 5 , 1465.

1986, 25, 1111.

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87 88

89 90 9 1

92

93

94

95 96 97

98 99

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102

103 104

105 106 107 10 8

109 110 111 112 113

114 11 5 116

117 118

119

12 0

12 1

122

123 124 12 5 126

12 7

H. C. Brown and S. M. Singh, Organometallics, 1986, 5, 998. H. C. Brown, 8 . M. Singh,and M . V. Rangaishenvi, J. Org. Chem., 1986, 51, 3150. H . C. Brown and S. M. Singh, Organometallics, 1986, 5 , 994. D. P. P h i l l i o n , R. Neubauer,and S. S. Andrew, J. Org. Chem., 1986, 51, 1610. J. Altman, H. Bohnke, A. Steige1,and G. Wulff, J. Organomet. Chem., 1986, 309, 241. T. Shinbo, K. Nishimura, T. Yamaguchi,and M. Sagura, J. Chem. Soc., Chem.

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B.-L. L i and R. H . Neilson, Inorg. Chem., 1986, 25, 361. H. J. Bestmann and T. Arenz, Angew. C h e m . I n t . Ed. Engl., 1986, g, 559. V. Hobel, H. Noth,and H. Prigge, Chem. Ber . , 1986, 119, 325. S. Kerschl and B. Wrackmeyer, Z. Naturforsch. , B: Anorg. Chem., Org. Chem., 1986, e, 890. S. Kerschl and B. Wrackmeyer, J. Chem. SOC., Chem. Comm., 1986, 403. B. Wrackmeyer, J. Organomet. Chem., 1986, 310, 151. B. Wrackmeyer, J. Chem. SOC., Chem. Corn., 1986, 397. A. Sebald and B. Wrackmeyer, J. Organomet. Chem., 1986, 307, 157. A. Sebald, P. Seiber l ich,and B. Wrackmeyer, J. Organomet. Chem., 1986, 303, 73. A. Sebald and B. Wrackmeyer, J. Organomet. Chem., 1986, 304, 271. G. E . Herberich and E . Raabe, J. Organomet. Chem., 1986, 309, 143. P. Paetzold, N. Finke, P. Wennek, G. Schmid,and R. Boese, Z. Naturforsch , B: Anorg. Chem. Org. C h e m . , 1986, 9, 167. G. E . Herberich and H. Ohst, J. Organomet. Chem., 1986, 307, C16. G. E. Herberich, W. Boveleth, B. Hessner, D. P. J. Koffer, M. Negele and

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U. Zenneck, L. Suber, H. Pritzkow,and W. S ieber t , Chem. B e r . , 1986, E, 971. K. Geil ich and W . S i e b e r t , Z. Naturforsch., B: Anorg. Chem., Org. Chem., 1986, *, 671. T. Kuhlmann, S. Roth, J. Roziere,aud W. S i e b e r t , Angew. Chem.,Int. Ed. Engl., 1986, 25, 105. G. Schmid and F. Schmidt, Chem. B e r . , 1986, 119, 1766. K . Lammertsma, J . Amer. Chem. SOC., 1986, 108, 5127. C. A. Taylor, M. C. Zemer,and B. Rameey, J . Organomet. Chem., 1986, 317, 1. P. H. M. Budzelaar, S. M. van d e r Kerk, K. Krogh-Jespersen and P. V. R. Schleyer, J. her . Chem. SOC., 1986, 108, 3960. R. 8. Cragg, T. J. Millar,and D. 0". Smith, J . Organomet. Chem., 1986, 302, 19. -


128 129 130 131 132 133

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Carbaboranes, including their Metal Complexes

BY T. R. SPALDING

1 Introduction, -Review Articles and Theoretical Aspects

The general layout of this chapter follows last year's rep0rt.l Compared to 1985, the literature on carbaboranes

increased substantially whilst that on their metal derivatives

decreased in 1986. Extensive reviews have appeared on complexes with

borabenzene2 and other r-bonded B-containing l i g a n d s S 3 Structural studies of metallacarbaboranes have been reviewed in general4 and compounds containing the (n5-Cp)Fe unit have received particular attention.5 The second part of a review of metallaboranes (containing >B8 atoms) was published.6 New metal catalysed7 and metal assisted oxidative fusion* routes to carbaboranes and their metal complexes have been discussed. Abstracts of dissertations on metal vapour synthesis of

inetailacarbaboranesga ana the kinetics of 1,2-C2B10H12 formation have The use of carbaborane-siloxanes in high

temperature g.1.c. has been reviewed.1° -- 1 . 1 . Theoreticai Aspects.- The MS-X, method was applied to [i312H12l2- and [C2BgH11I2- and the results analysed in terms of the distribution of group charges .I1

The relative stabilities of c l o s o CzBn-2Hn ( ~ = 5 to 1 2 ) isomers were studied by topological charge calculations based on net atomic electron populations from extended Huckel calculations.l2 Perhaps surprisingly the results were in

excellent agreement with published experimental data.

- -

From extended Huckel and ab initio (STO-3G) calculations it

was concluded that diamond-square-diamond (DSD) rearrangements are blocked f o r C2B3Hg13a but double DSD processes are feasible for C2B7Hg and [BgH9]2-.13b No rearrangements of these species have been observed experimentally. A semi-empirical and a b initio study (3-21G geometries, MP3/6-31G and HF/6-31G* energies)

of the possible dimerisation of borirene, (CH)2BH, to 1 , 4 - d i b o r a c y c l o h e x a - 2 . 5 - d i e n e o r nido-2.3,4,5-C482Hg showed the



former process to be facile.14 However no path to the latter thermodynamically more stable isomer couid be identified. Five

isomers of borirane, (CH2)2BH, were studied by ab initio methods (3-21G geometries, MP4/6-31G** energies) .I5 It was concluded that the closed ring form is a stable minimum on the potential surf ace.

2. Carbaborane Synthesis, Characterisation and Reactions

2.1. CA-Carbaboranes.- A new route to nido-4,5,7,8-MeZEtZC4B4H4 uses metal promoted (NaH/NiC12) insertion o f but-2-yne into 2.3-EtzC2BqHg. l6

The synthesis and characterisation (including X-ray

analysis) of Li salts of a 1.3-diboretanediide ( l p 7 and a

bis-B-NMe2-derivative o f 1,2-diborabenzene (2) were reported.18 The former is dimeric end contains a layer of four Li atoms between two puckered C~Bz-rings. The latter reacts with TMED t o

give a tripie ionic system with two [Li(TMED)]- cations capping

opposite faces of a pianar [1.2-CAH4(BNMe2)2]2- anion. In the chemistry o f 1.3-dibo-etanes (3),19 .Y-rilv anaiysis showed

( ? r 1 2 ~ ) ~ { C ( H ) S i n e 3 ) s ( N P r i 2 ) { C ( ~ ) S i ~ e 3 ) to be puckered whereas ~ P ~ ~ ~ N ) B ( C ( S ~ M ~ ~ ) ~ } B ~ S P ~ : ~ ) ( C I A U P P ~ ~ ) ~ ) is pianar. -- 2.2. C7-Carbaboranes.- A Me3Si-group I S removed from n i d o

2,3-(Me3Si)2C2BgHg by reaction with Na[HFz] at 14OoC to give z-(Me3Si)CzB4H~ ( 4 ) q u a n t i t a t i v e l ~ . ~ ~ The structure of (4) was determined by electron diffraction.

i

I 1

Reaction o f Et3NBH3 with nido-2,3-Et2C~BgHg at 140°C afforded closo-2,3-Et2C2B5H5 which underwent isomerisation at 32OoC to 2.4-Et2C2BgHg. 21

Rearrangement of 5-Me-6-Cl-2.4-C2BgH5 to a mixture o f all eight possible B-substituted isomers was studied at 295°C.22 Rates and the sequence o f rearrangements were noted and shown to

be consistent with a DSD-mechanism. The relative stabilities of the isomers were discussed.

Electrophilic (D.Cl,Br,I,SH) and nucleophilic (Bu) substitution of a r a c h n o 4,6-C2B7H13 gave 3- o r 5-derivatives and 3.5-X2-4.6-C2B?Hll for X = D , C 1 . Br, I 23

Several syntheses o f C2B8-Carbaboranes have used B5Hg as a starting reagent. Both nzdo 5.6-C288H12 and nido- 3,6-(Me)2-J.6-C~a~Hlo we-e ?roauced b v reacting BgH13OEtZ (formed in s i t u ) with acetyiene or but-2-yne r e ~ p e c t i v e l y . ~ ~ Addition o f

2.6-iutiaine to a rnix:ri?e 0 : oilt-2-yne and 1,2'-(B5H8)2 gave

Carbaboranes, including their Metal Complexes

R’ R’

R = But , R ’ = SiMeg

R‘ R”

X R-BxB-R R‘ R”

H90

cs) Figure 1. 6-CMe3Sil-6,9-C28sH13

[Rbproduced with permission f r o m Inorg. Chem.,

1986, 25, 43511

41


~ l o s o - 1 . 2 - ( M e ) ~ - 1 . 2 - C 2 B g B Q . ~ ~ Reaction of E5Hg an2 nido-i2,3-(Me3Si)2-2,3-C2B4Hsj- afforded arachno-6-(Xe3Si)- 6,9-C2BgH13 (51, Figure 1. which was characterised using X-ray analysis.26 The cage geometry was similar to [BloH14]2- with two bridging hydrogens.

Selective cage degradation of [NH4]2[1,2-(S)2-1,2-C2BloH~o] to [ 7 , 8 - ( S H ) 2 - 7 . 8 - C 2 B g H 1 0 ] - (6) is accomplished on refluxing in ethanol in the presence of 1.2-C12C6H4.27 Reaction o f ( 6 ) with aqueous [ 1 3 ] - gave anti-[!CBgH1OCSSCBgH1o~]z- ( 7 ) .

the structures of (6) and (7) are now published. Details o f

Addition of an exo-BHg group occurs when excess Et3NBH3 reacts with Cs[7,8-C2BgH12] at 2OO0C giving [ I - H ~ B - ~ , ~ - C ~ B ~ O H ~ I J - . ~ ~ Further reaction with donors ( L = Me2S, Me3N. Et3N, py) yields I-LBH2-1,2-C2BioH11 products. In contrast, reaction of [7,9-C2BgH12]- with Et3NBH3 gave l-Et3NBH2-1,7-C2B10H11 in low yield.

( 8 ) have been synthesised.29 Subsequently cyclopentene and cyclopentane derivatives were isolated. Sealed tube pyrolyses

(200-275OC) o f dialkyl acetylenedicarboxylates o r trialkyl methanetricarboxylates and 1,2-C2E10H12 (or C-substituted aerfvatives) gave mainly 9-alkyl-1,2-C2EJ1oH11 products.30 Alkylation o f 1,2- and 1,7-C2B10H12 with PriX (X = C1, Br) in the presence of AlCl3 gave 4-, 8 - , 9- Pri and 8- and 9- Prn p r o a u c t ~ . ~ ~ ~ Nixed Pri and Prn derivatives were formed from PrnX. The migration o f the 9-Pri group in the above compounds in the presence of AlC13/HCl was studied.31b Insertion of :CR2 (R2 = F2, C12, HPh, H2) into B-H bonds of 1,2-C2B10H12 follows pseudo first order kinetics.32 Syntheses of l-methylallyl,33 l-ethynyl,34 and 9-(Cl2C=C(Me))- derivatives3b o f 1.2- and 1,7-C2B10H12 are reported.

derivatives with l-Ph-2{C(O)C1}-1,2-C2B10H10 have been studied.36 Several compounds o f the type RCBloHloCCH2CH2X have been

prepared with X = O H f o r 1.2- or 1 , 7 - ~ a r b a b o r a n e s , ~ ~ ~ or Si(O2R')3 for the 1 , 7 - ~ a r b a b o r a n e . ~ ~ ~ Disubstituted { X ( C H ~ ) ~ C ) ~ B I O H ~ O systems were also described for X=OH, &=2,37a and X=0.5(02P3N3C14), a=1.38 Polymerisation of the latter was reported.

The first compounds containing bridged B and C cage atoms

The kinetics of acylation of PhNH2 and 2-substituted

B-bonded carbaboranylphosphonate esters {9-(Me0)2P(O)-) o f

Carbaboranes, including their Metal Complexes 43

1.2- and 1,7-C2B10H10 are proauced on U . V . irradiation of

(C2B10H11)2Hg in (Me0)3P.39 Compounds of the type RR'P(X)SR'' (R" = 1,2- or 1,7-carbaboranyl or derivatives: X = 0 , s )

containing P bonded to the 9-B atom were reported.40 Addition of

Li[PPh2] to ~ - M ~ - ~ - R C = C H ~ - ~ , ~ - C ~ B ~ O H ~ O (R = H , Me) followed by Me1 gave 2-CH(R)CHzPPh2Me-containing phosphonium salts.41 A variety of metal complexes containing carbaboranylphosphine ligands have been reported including P ~ ~ P C B ~ O H ~ O C C H ~ R (R = MeS, Et2N) complexes of M o and W carbonyls,42a P ~ ~ P C B ~ O H ~ O C C ( M ~ ) = C H ~

complexes of Rh,42b and Pd complexes of Ph2PCBloHloCR (R = H, Ph2P. (NMe2)2P)42c*d some of which also contained the

[1,2-(S)2-1,2-C2BloH10]~- ligand.42d

derivatives (SH, S R , SCN. SCl, S(O)R2, S(0)2R2) were reported,43 Up to four SH-groups could be introduced using S2C12/AlCl3 reagents.

A number of S-containing B-substituted 1.2- and 1,7-C2BloH12

Fluorination o f 1,2-C2BloH12 with SbFg/N(CzFg)3 gave di-(9,12-), tri-(8,9,12-) and tetra-(8,9,10,12-) fluoro

derivatives.14 C2B10€!10. Chlorination of 1.7-C2BloH12 with Na[OH]/CC14 in the presence of [Et3(PhCH2)N]Cl afforded 1.7-C12-1,7-C2B10H10.45

Hg(C2BloHll)2 is accomplished with catalytic amounts of [RhCl(PPh3)3] in hexamethylphosphoraride.46

Studies of polymers containing C2-carbaboranyl groups include some based on polyarylacetylenes,47a polyamides and

related compounds,47b-d and a copolymer of acryloferrocene and carbaboranylstyrene.47e An investigation o f the kinetics and

mechanism of the radical polymerisation of diphenylcarbaboranes

48a and a study of the radical polymerisation o f

carbaboranylne thylne thacr ylat e have been reported. 48b --- 2.3. C m r 1 a b o r a n e s . - A n improved yield o f nido-6-iI3N-6-CBgH11 was obtained from [B10H13CNI2- via the reaction of 6-Me2C=NH-6-CBgH11 with aqueous K[OH].49 Replacement of NH3 by H-, SMe2 and NWe3 was reported. 2.4. Physical Properties and Uses.- Empirical rules f o r predicting the relative llB n.m.r. chemical shifts in closo

boranes and heteroboranes have been devised.50 [llB-llB]COSY has

been used to elucidate cage structures e... 8rdChna-6-(Me3Si)-6,Q-C2B8H13,26 and nido-CBgH12 (9).51 The

The 1,7-carbaborane produced only 9.10-F2-1,7-

Synthesis of 9,9'-(1',7'-C2B10Hll)-l,7-C2BloHll from


<. Ni

. i i

Ni n Ni

Ni . . b

Scheme 1


latter had two H-bridges between B(4) B(5) .and B(9), and another

between B(6) and B(8).

Both the l0B and llB n.m.r. spectra of 1.2-D2-1,2-C2B10H10

were used in a study of B quadrupole coupling.52a Spin-lattice

(TI) relaxation times were meaured. It was concluded that T 1 values were dominated by the quadrupolar relaxation mechanism

whereas there was a substantial boron-boron scalar contribution

to T 2 times. The quadrupole coupling constants from this solution study were in good agreement with the data from a solid

state B n.q.r. investigation52b and a solid state 13C, l0B, and

llB n.m.r. study.53 Relaxation effects in carbaboranylpolyesters

have been investigated from -196 to 450°C.54

Raman spectroscopy was used t o assign 8-H and C-H modes in

C2Bio-carbaboranes and polysiloxane-carbaborane polymers,55 and to study phase transitions in C2B8H10.56

between 300-250°C have been reported.57 Mass spectra of the 1,2-, 1,7-, and 1,12-C2B10H12 isomers

The ignition characteristics of l-Bu-1,2-C2B10Hll have been studied.58 Pyroiysis-gc was used to investigate the products of

thermal decomposition of carbaborane-diphenylsiloxane

Several studies of the thermal stability or thermal oxidation resistance of carbaborane-containing compounds have

been reported.60a-e Related t o these are investigations of the

use of carbaborane additives to produce heat resistant coating

materials.61a-c layers. 6 2

Carbaboranes were used to produce B-doped S i 0 2

The [CB11H12]- ion interacts with the iron atom in [Pe tetraphenylporphyrinate]+ v f a a weak unsupported Pe-H-B

bridge (Fe-H = 1.82(4);).63

1,12-C2B10Hll) produces R and HgR radicals.64 Photolysis of 9-B bonded [HgRz] compounds (R = 1 , 2 - , 1,7- or

__ 4. Cape Meta/lacarbaboranes

... 4.1. . -. C c a n d Cs-Ca-CD-aboranyl 1igands.- The full experimental procedure for the preparatlon of the f i r s t polydecker compound

(10) [ N I ( M ~ ~ C ~ B Z H ) ] ~ , Scheme 1 , has been published.65 This remarkable compound is reported t o be stabie at 5OOOC but is

46 Organometailic Chemttry

I

.. Ni H

‘X&B- 1

Scheme 2

F i g u r e 2 . CICNe3Si12C2BQH4)21


02-sensitive and insoluble in organic solvents. Other complexes

containing planar r-ligands include a (n4-l,5-cod)Co-coaplex of a

C3BN-ligand,66 compounds of Mn, Fe. Co,67a and Rh6'lb with CqHqBR ligands and the triple decker [ ( C O ) ~ C ~ { I ~ - C ~ H ~ B ( P ~ ) } F ~ C ~ ] - species

which was structurally characterised (X-ray) .68 Iron coaplexes

of the 1,3-diborabenzene ligand, l,3-(NPri2)-1,3-B2CqX4 69 and Ru complexes of 1,2-(NMe2)2-1,2-B2CqHq have been prepared.18 Several complexes of Pe, Co and NI based on the

l - p h e n y l b o r a - 2 , 5 - c y c r o h e x a d i e n e (LH) ligand were described which

had n6-L, n5-LH or n4-LH2 to M bonding.70 Paramagnetic, [{1,4,6-(Me)3-2.3-(R)2-2,3,4-C3B3H)ZNiI, R=Me

or Et, (ll), complexes were prepared from [Ni(CgH4)3] and excess of 1,3-(Me)2-4.5-(R)2-1,3-diboroles, Scheme 2.71 X-ray analysis showed (11) to be centrosymmetrlc.

4.2. C7-Carbaboranyl 1igands.- Compounds of Si(II), Si(IV),72

Ge(II), Ge(IV),73 and Sn(II)74a were prepared by reaction of MCl4 (M=Si,Ge) o r SnCl2 with the nido-[(Me3Si)2C2B4H5]- ion. The

Si(I1) complex was an air sensitive liquid but the Si(1V) product

was air stable. The structure of the Si(1V) compound (X-ray) is shown in Figure 2 and the Ge(1V) compound was analogous. In both

molecules the M-C bonds were significantly longer than M-B bonds

indicating some slippage towards the B3-bonded atoms. Details of the structures (x-ray) of [2-(Me3Si)-1,2,3-Sn(II)C2B4H5] (12) and [l-(bipy)-2,3-(Me3Si)2-1,2,3-Sn(II)C~B4X4] (13) have now been published.74a Comparison of these structures shows that whereas

the Sn-C bonds in (12) were slightly but significantly longer

than the Sn-B bonds {in a similar sense to the Si(1V) and Ge(1V)

compounds above}, the Sn-C bonds in (13) were much longer

[2.70(1) and 2.75(1) i] than the Sn-B bonds [2.44(2), 2.37(2),

and 2.52(1) 11. This is a function of the increased electron

density at the Sn atom on bipy coordination and has analogies

with the [l-(bipy)-2, 3 - M e 2 - 1 . 2 , 3 - S n C 2 B ~ H ~ ] complex previously reported.74b

The c ~ o ~ o - ~ l . l - ( d i p h o s ) - 1 , 2 , 3 - N i C 2 8 q H g ] complex was

suggested to be formed v i a a nido-[4,5-v-(NiX(diphos)}-2.3-

C2BqH71 intermediate in the reaction of [ N i X ~ ( diphos)] (X = C1, Br) and [C2B4H7]-.75 Low temperature (-78OC) n.m.r. evidence was obtained for the intermediate when X = C1 but not Br.

Reactions of thermally generated F e , Co, or Ni atoms with nido-2,6-C2B7H11 in the presence of hydrocarbons (C5H6, tolH.


6 Figure 3. 16-111 -mesH)-6,9,10-FeCZB7Hlll

(Reproduced with permission from Organometallics. 1985, 2, 3271 . -

Figure 4 .

CReproduced with permission f r o m Organometallics, 1986, 5, 3271 Cll-Ln3-C4Me4H1 -5,7, 8-1Me13-ll,7, 8, 10-NiC3B7H71


mesH, or but-2-yne) have been investigated.76 Iron atoms,

carbaborane and tolH gave the n6-arene-Fe complexes

closo-[2-(n6-tolH)-2,6,9-FeC2B7Hg] (14) and the 2,1.6-isomer ( 1 5 )

whose structures were determined (x-ray). Compound (14)

converted t o ( 1 5 ) on heating (75OC). Replacing tolH by mesH

afforded the equivalent (n6-mesH)-Fe compound of the 2,1,6-isomer (16) and the n i ~ o - [ 6 - ( n 6 - m e s H ) - 6 , 9 , 1 0 - F e C ~ B 7 H ~ l ] complex (17), Figure 3. The structure of ( 1 7 ) was related to B10H14 with two

Fe-H-B bridges and adjacent C atoms. With Co atoms, cyclo-

pentadiene and carbaborane. the new clusters

[ 2- ( n5-Cp) -2,l. 4-CoC297Hgl (18) , and [ 4- ( n5-Cp) -4,2,3-CoC2B7Hg]

(19) were isolared together with the known cospounds

!2- (q5-Cp)-2, 6,9-CoC2B7Hg] ana [ 8 - (n5-Cp) -8,6,7-CoC2B,Hg] . Rearrangement of (18) to the 2.1,6-CoC2-isomer occurs on heating

(7OOC). Reaction of' nickel atoms with the carbaborane, tolH and

but-2-yne gave only one characterisable product,

[ 11 - ( n3 -C 4MeqH ) -5,7 ,8- ( M e ) 3- 11 , 7 ,8,1O-N i C 3B 7H 71 ( 20 ) , Pi gure 4. The Ni is bonded to a n3-cyclobutenyl unit and a C2B2-section of

the CgB7-cage in a most unusual 11-vertex cage geometry. Clearly extensive involvement of the but-2-yne reagent is implicated in

the formation of both the C4- and C3B7-units.

6.9-C2B8H10] has been reported.77 The Pt atom adopted a square planar configuration in its bridging position.

The X-ray structural characterisation of [6,9-~-(Pt(PPh3)2}-

A novel coaao-aluninacarbaborane (21), Figure 5, was

isolated from the reaction of cIooo[3-Et-3,1.2-AlC~BgH11] (22) with C0.78 The complex is formally a dimer of (22) but adopts a

zwitterionic [AlEtz] [A1(n5-C2B5Hll) 21 composition. One A 1 atom occupies a nearly symmetrical 3.3'-commo-position sandwiched

between the parallel C2B3 faces of the carbaborane ligands, the other is part of a doubly 9-H bridged Et2Al group.

The c o i n o [ 3 , 3 ' - S i ( 3 , 1 , 2 - S I C 2 B q H 1 1 ) 1 complex (23), was prepared from Sic14 and Lf2[7,8-C2BgH11J.79 It is isoelectronic with the commo section of (21). Reaction of (23) with two

equivalents of LIIBun] selectively deprotonated two C-H bonds.

Addition of the Pt(PEtg)z-unit t o the tungsten complex

[PPNI[W(CR)(CO)2(1,2-Me2C2BgHg)l ( R = p - t o l ) by reaction with [tran~-PtH(acetone)(PEt3)2][BP4] produced (24) Scheme 3.80 The structure (x-ray) showed a number of novel features including a

broken C-C bond and distortion of the 95 ring below the C2B3 face


Flgure 5. 3 , 3 ’ A l t ~ e ~ o - 8 , 9 - L ~ - H ) 2 A 1 E t ~ ~ 3 , 1 , 2 - A 1 C 2 B ~ ~ ~ ~

(Reproduced w i t h permission from J. Am. Chem. S o c . , 1986,

108, 53671

~ 3 ’ , 1 ’ , 2 1 - A 1 C 2 B g H 1 1 ~ ~

-

___+

0 0 (241 OB OBH *CMe (25)

Reagents ( i ) [truns- PtH(acetone1 (PEt3 [BF4] ( i i ) CO or PMe3

Scheme 3

Carbaboranes. including their Metal Complexes 51

leading to a W-B interaction, transfer of the CR ligand to B(4) as the (CH2~-tol)-gro u p , and formation of W=Pt bond. Further reaction of (24) with CO or PMe3, Scheme 3, afforded (25) in which the C-C bond had reformed to produce the usual carbaborane geometry. The tungsten atom was now bonded to three terminal ligands ((C0)zL) and had a single bond to Pt which was H-bridged, and Pt was bonded to the carbaborane cage v i a B(3).

Reaction of [Fe(cod) (n5-Cp)l with 2 , 3 - M e 2 -2,3-C2B~Hg in the presence of arenes (CgHfj, tolH, o-xylene, napH) gave c l o s o -

!l-(n6-arene)-2,4-Me2-1,2,4-FeC2B~Hg] complexes.81 Displacement of the arene ligand from the naphthalene-Fe compound by CO or P(OMe)3 gave the corresponding 1-(L)gFe-complexes. C l o s o -

[3-(L1)-3,1,2-RuC2BgHli] compounds were prepared from Tl[TlC2B~H111 and [RUC12(L')2](L'=CfjHe) or IRuC12(Lt)(THP)] {L'=(CO)3). Both the (tolH-Pe) and ( C ~ H f j - R u )-comp~exes were structurally characterised by X-ray methods.

(28). Figure 6, has been measured (x-ray, 185°C).82 The cisoid conformation and direction of slipping were analysed in terms of results from extended Huckel calculations on (26) and [3-(n5-C5H5)-3,1,2-CoC2B9H11] whose structure was also determined at 185OC.

The slippage of the Co atom in [ 3 - ( n 5 - C ~ H7)-3,1,2-CoC2B~Hll]

The structures (X-ray) of three partly halogenated commo- [3,3'-Co(3,1,2-CoC2BgH11)2]- complexes have been reported.83 None exhibited the disorder present in the parent conplex and in all cases the C2B3 faces of the carbaboranyl ligands were staggered. However in the mono-lodo derivative, Figure 7, c o n n o - [ 3 , 3 1 - C o ( 8 - I - 3 , 1 , 2 - C o C ~ B ~ H ~ ~ ) ( 3 ' , 1 ' , 2 ' - C o C ~ B ~ H ~ ~ ) ] ~ 3 a the Co atom was not at a pseudo centre of symmetry v i m a v l r the two C2B3 faces whereas in the b i s - ( 8 - 1 - 1 , 2 - C 2 B ~ ) - * ~ ~ and b i ~ - ( 8 , 9 , 1 2 - B r 3 - 1 , 2 - C 2 B g ) - ~ ~ ~ derivatives the Co atoms were at centres of symmetry. In [8,8'-~-(MeOC(o)CH2S)- c o r n o - 3 , 3 ' - C o ( 3 , 1 , 2 - C o C ~ - B ~ ~ ~ ~ ] (27, X-ray) the carbaboranyl ligands are linked through the S atom.84 The angle between the planes containing the C2B3 faces is 16.fjo, a value between those found In related unbrldged (3.8O) and 0-bridged (28.2O) complexes.

The orthoaetallated [3-(Ph2P~gHq)-3-(PPh3)-3,1,2-~hC2BgH111 complex has been atructurally characterised by X-ray aethods.85 as has [3-(n4-cod)-3,1,2-PdC~B~ii11].86 In the latter study the slip and fold distortions about the PdC2B3-section were discussed.


Figure 6. t 3 - [ 1 l ~ - C ~ H ~ 1 - 3 , 1 , 2 ~ C o C 2 B g H l 1 1 (Reproduced w i t h permission from Organometallics, 1986, A , 7601

Figure 7. C ~ , ~ ' - C O ~ ~ ~ T - ~ , ~ , ~ ~ C O C ~ B ~ ~ ~

CReproduced with permission from Acta

a 1 ( 3 ' , 1 ! , 2 ' - C ~ C 2 B g H 1 ~ ~ 1

Crystallogr. 1986, E, 30 I


Estimation of the Taft constant for [3-(n5-Cp)-3,1,2-

FeCzBgH111 suggests that this species has strong electron donating properties .87

The synthesis and catalytic properties of polymers containing carbaborane-bonded Rh have been described.e8

- 4.3. C1-Carbaboranyl l&gmds-.- Reaction of 6-H3N-6-CBgH11 with the (n5-CpCo) moiety gave [1-(n5-Cp)-2-(H3N)-1 ,2-CoCBgHg]

(28).49 Methylation of (28) gave the 2-Me2NH-derivative and deprotonation afforded the 2-H2N-containing anion.

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R * Saive 9 _4ngeWw.~Chel...1.nt,.-.Ed *..-..KCg.JLL* 1986 9 251 165 *

C16.

143.

_Che?L:.-..I nt.LEd, ... Eng?.l.* 1986 1 2 4 . 1099 '

and S . S . C Chu J,Chem,~._Socl~,_Chepl.,_.._C_o_m-~un, 1986 I 142 1 . s * c . c . Chu . 2.1 _..e.m.:-._.chem..,..s.~~~, 1986 1 Lei?* 6050

S.C.C. Chu. and R . H . Herber, Organometallic,~-, 1986, 5, 772; (b) A.H. Cowley, P. Galow, N.S. Hosmane. P. Jutzi, and N.C. Norman, J. Chen. SOC, Chem. Comnun., 1984, 1564.

75. L. Burton and P.K. Rush, Inorg,---C"h-em,, 1986. 25, 91. 76. J.J. Briguglio and L.G. Sneddon, ~rganometall.&c~, 1985, 2,

327. 77. G.A. Kukina, M.A. Porai-Koshits, and V.S. Sergienko,

_K_o_o_rd. KhLm,, 1986, 12, 561. 78. W . S . Rees. D.W. Schubert, C.B. Knobler. and M . P . Hawthorne,

J. Am. Chen. Soc., 1986, .lO-g, 5367. 79. W.S. Rees, D.M. Schubert, C.B. Knobler, and M.F. Hawthorne,

^__l____l_...-_-_ J. Am. Chem. SOC . , ~ 1986, j-02, 5369. 80. M . F . Attfield, J.A.K. Howard, A. N. de M . Jelfs, C.M. Nunn,

and F.G.A. Stone, J. C h e k . S o c . , C ~ e m _ C o m m u n . , 1986, 918. 81. M.P. Garcia, M. Green, P.G.A. Stone, R.G. Sonerville,

A.J. Welch, C.E. Briant, D.N. Cox, and D.M.P. Mingos, J. Chee. SOC.. Dalton Trans., 1985, 2343.

82. D.E. Smith and A.J. Welch, Organometallics, 1985, 5, 760. 83. (a) P. Sivy, A. Preisinger, 0. Baumgartner, P. Valach.

B. Koren, and L. Matel, &r.a-&ystallogr. 1986, S B , 3 0 ; (b) i d e a , ibid, 1986, m, 28; (c) idem, ibid. 1986, C4&, 24.

663.

Crystallogr., 1986, m, 159.

84. I. Cisarova and V. Petricek, Acta Crystallogr., 1986, w, 85. C.B. Knobler, R.E. King, and M.F. Hawthorne, Ac&

86. D.E. Smith and A.J. Welch. Acta Crystall_o_gr., 1986, C&g, 1717. 87. C.I. Zakharkin and V.V. Kobak. Is!. Akad,_-Kgak SSSR, Ser.

88. V.N. Kalinin, O.A. Mel'nik, A.A. Sakharova. T.M. Frunze, _KhCmA, 1985, 1449.

L.I. Zakharkin, N.V. Borunova, and V.Z. Sharf. Izv. Akad. I___ Nauk SSSR, Ser. Khiqr,, 1985, 2442.

5 Group 1 1 1 : Aluminium, Gallium, Indium and Thallium

BY P. G. HARRISON

Besides the dictionary of organometallic COmpOUndS of aluminium, gallium, indium and thallium', an essential companion for all researchers in this area, two other extremely useful review articles have appeared. One deals comprehensively with the application of organoaluminium reagents in selective synthetic reactions such as the organoaluminiunrpromted Beckmann rearrangement of oxime SUlphOMteS, new syntheses of polyamiao macrocycles via reductive cleavage of aminals and amidines by diisobutylaluminium hydride, the diastereoselective cleavage of chiral acetals by organoaluminium compounds leading to optically- active secondary alcohols, allyllc alcohols, and B-substituted carbonyl COmpOUnd6, and biomimatic terpene Syntheses*. The other describes the structure and bonding in arene complexes of univalent gallium, indium and thallium3.

The infrared spectrum of Al(C0)Z observed in deposits of aluminium atoms and CO in adamantane at 77K exhibit6 symmetric and antisymPetric CO stretching mode6 at 1985 cm-' and 1903.8 cm-l. The infrared spectra also indicated evidence for the formation of the binuclear species AlrCO and Alz<CO)r4. The matrix isolation technique has been employed to show that ground state aluminium atoms react with methane, though less efficiently than the spontaneous reaction observed with boron, whilst gallium and indium atoms do note. However, 60- controversy exists as to whether or not photoactivation is necessary". Electron spin resonance studies of the reaction of ground state aluminium atoms with buta-lB3-diene show that two major paramagnetic species, a 0-

[For re fe rences see page 77 57


Scheme 1

R’ I

/=%c22 I ’\

A1

4 A 1 W e 3

Scheme 2

Group III: Aluminium, Gallium, Indium and Thallium 59

bonded aluminium cyclopentene and an alUminiUP6Ub6titUted allyl, are formed In adamantane at 77K7.

Detailed synthetic procedures for the preparation of trisC <trimethylsilyl)methyll aluminiunP, bromobis- C <trimethylsilyl)~methyll aluminiumm, trisC (trimethylsilyl)methyllindi~rn~~, and cyclopentadienylthalliumll have been described in Inorganic Syntheses. Ultraeonics has been employed to greatly accelerate the direct syntheses of trimethyl- and triethylaluminium7= * Aluminium powder reacts with methyl iodide or ethyl bromide in the presence of iodine to afford the corresponding alkylaluminium sesquihalide, which may then be converted into the trialkylalane by treatment with either triethylalane or ethylmagnesium bromide (prepared fn s f t o ) (Schema 1). The initial formation of the aesquihalide 1s complete within only 30 minutes for the methyl derivative and within 2 hours for the ethyl homologue. Isolated yields of trlmethylalane obtained by the ultrasound method at room temperature can be a6 high as 96.4% (cf. 0% by stirring in the absence of ultrasonic irradiation); yield8 of triethylalane were somewhat lower <up to 76.2%) (cf 1.4% with stirring). Mixed magnesium-aluminium alkylsl* and trialkylgallium compounds1S have been obtained by the direct method by simply heating the appropriate reactants. Thus, heating aluminium and magnesium with alkyl iodides at 80-110' afford the mixed alkyl, AlnMgm,R~n+~m (R = CA-Clo alkyl; n = 1-5; m = 1-4). The gallium alkyls are obtained by the alkylation of a gallium-magnesium amalgam <mole ratio Ga: Mg: Hg 1: 3: 0.2) at elevated temperatures. (eg trimethylgallium can be obtained in 75% yield from the amalgam and methyl iodide in diisoamyl ether at 60- 8 0 ' . An alternative preparation of trimethylgallium involves the methylation of GaCla with methyllithium In diethylother giving the etherate, M e a G a . EtrO, treatment of which with triphenylphosphine yields the adduct, MeaGa.PPh3, which dissociates at 80-90' and 10- * torr to afford trimethylgallane in 71' yield1=. Twa methods have been employed for the synthesis of trinuacitylaluminium, metathesis between aluminium(I1 I ) chloride and solution6 of mesitylmagnesium bromide or dimesitylmagnesium in thf17 or by metal exchange between dimesitylmercury and aluminium metalla. The Grignard method has also been used to obtain trimeityl- gallium1*. From thf solution triPesitylaluminium ciystallises a6 a thf adduct (trimesitylgallium form no stable adduct at room


temperature), which easily loses thf under evacuation at elevated temperatures giving the unsolvated compound. Addition of pyridine givee the quite thermally stable monopyridine adduct, whilst further mesityllithium in thf results in the formation of the complex salt, C Li Cthf )41 C Almesrl . Redistribution with one or two mole6 of aluminium<III) chloride in thf affords mesitylaluminium dichloride and dimesitylaluminium chloride, both a8 thf adduct6I7. The structures of both trimasitylaluminium'~ and trime~itylgallium'~ have been determined. Both are monomeric in the crystal with trigonal planar coordination about the metal atoms and the malty1 group adopting a propeller-like conformation. The lac CP/WS spectra of trimesitylaluminium show that the ortho methyl groups are magnetically nonequivalent in the solid state as a result of crystal packing, but become equivalent in solution when these constraints are removed. Facile redistribution of triethylaluminium with MeaSiCl occurs at 30' in toluene affording an 85% yield of EtsAlCFO. Trimethyl- and triethylindium undergo ligand exchange at room temperature under argon giving the mixed alkyl, EtWeSIn"'.

l D m r has been employed in the study of solution equilibria and structure in solution. ' H nmr studies of diisobutylaluminium indicate the presence of a small amount of a second oligomer in addition to the well-documented trimer in the neat liquid as well as in mixtures with inert solvents=". The simple aluminophosphine, XesAlPMePh, has been prepared by an elimination- condensation reaction between MeZAlH and PMePhH. In benzene solution the compound exists as a trimer, hodver the complexity of the spectra suggest the presence of several different 160merS due to different ring conformations and/or different orientations of the methyl and phenyl groups. The degree of association changes as the benzene solvent is remved leaving an amorphous, possibly polymeric, material which is no longer completely soluble in benzene. Sublimation of the amorphous material at 170' produce6 a transparent gla66 which is also only partially soluble in benzene. The trimer may be reformed by extensive heating with benzene. Kinetic studies confirm a second order reaction though complicated by equilibria, in which the initial intermediate is a monomeric HeSAlPWePh species. This in turn reacts with MesAlH and/or XezAlPMePh to eventually for the trimer'C3. The 6Ll{1H> Nuclear Overhauser Effect has been used to identify the protons

Group 111: Aluminium, Gallium, Indium and Thallium 61


close to the -Li nucleus in solutions of lithium hydro[ tr i s<tr imethyls i ly l>methyl l metalates of aluminium, gallium and indiue4. These compounds, like analogous boron derivatives, appear to exist in toluene or thf with hydrogen bridges between the Group I 1 1 metal and lithium as in (l), and which has been confirmed for the indium compound by an X-ray studyP1. That care and caution need to be exercised in the interpretation of nmr data has been amply illustrated in the ”Al nmr studies of solutions of

five-coordinated compounds of the type IE~z~A~OCHZCR~XIZ <R = H, X

= OMe; R = H, X = 1IIBt2; CR=X = 2-H4C=B). For these compounds the

6<”7Al) values exhibit no significant temperature dependence In the temperature range 310-ca. 2 2 3 K . Previous different observations in the latter case were attributed to background signals, and thus conclusions invoking equilibria between four- and five-coordinated species were erroneouszA.

The methylaluminium chlorides have been the subject of a detailed infrared studyzs. Spectra of the monomer species MezAIC1 and MeAlClS have been recorded by thermal dissociation of the corresponding dimers followed by isolation in argon matrices. Whilst the A1-C bond is of similar stability for all the monomers

Me*-,-,A1Cln <n = 0 - 2 > , the A1-C1 bond strength increases with increasing alkyl content. Several chlorine-bridged dimers were identified in studies of the dimsric compounds, and the following decomposition sequences:

MePAl&ls - MeaAlaClo + trans-MesAlrC1.a

were deduced to occur at temperatures of 350-450’ and 5 5 0 ’ ,

respectively . A s in previous years, many investigations have been

accompanied by structure determinations, mastly by X-ray diffraction. The crown ether, 12-crown-4, reacts with trimethylaluminium in toluene forming the adduct C AlXeald 12- crown-41. The molecule resides on a crystallographic centre of inversion, and, as required by symmetry, the four oxygen atoms are coplanar. coordination to aluminium were u n ~ u c c e ~ s f u l ~ ~ . Addition of caesium azide or <dibenzo-18-crown-6~potassium azide to

Attempts to utilize the remaining two oxygen atoms fo r


trimethylaluminium in aromatic solvents affords the complexes Cst Alde ~ B a l . 2p-xylene and t K(dibenzo-18-crown- 6)l CAl~Me~B~I.l.5~1-methylnaphthalene). In the former complex, the caesium atom resides on a mirror plane and is sandwiched by the two p-xylene molecules. The anion is disordered about a two- fold axis, and one of the 1-methylnaphthalene molecules in the

latter complex is also disordered about a centre of inversion and interacts with the potassium Ion. The other solvent molecule is present roughly in layers in the lattice and also exhibits disorder of the methyl substituent. In both complexes the AlMea groups of the anion exhibit a staggered conformation=H. Trimethylaluminium reacts with stoichiometric quantities of ci-

imino ketones to form the 2:l complexes (2) (Scheme 2). The reaction is complete in 30 minutes and depending on the

substitution pattern of the ligand some of the complexes are stable and isolable. The w,v-B,O-bridged coordinated a-imino

ketone ligand in crystals of <1) <R1 = Me; RY = R" = Ph) has the 2 configuration at the imine bond. In most cases, however, the 2:l

adducts could not be isolated because of rapid subsequent conversion to the stable ketone-alkylated products (3). The

structure of one example (R1 = +-Bu; R2 = H, R3 = Me) has been determined, confirming the general molecular structure with an

AlMes unit coordinated to the alkoxy oxygen atomzg. Triethylaluminium reacts with a variety of tetradentate Schiff-

base ligands in benzene/acetonitrile solution to give the monoethylaluminium compounds (4 ) - (7 ) . These complexes are stable

in the solid state in the absence of moisture, but react with moisture and anhydrous HC1 in solution to give ethane and the

corresponding hydroxyaluminium and chloroaluminium complexes, respectively. The structure of complex ( 4 ) has been determined, and the aluminium atom is displaced 0 . 5 4 0 A from the best least- squares plane containing the two nitrogen and two oxygen atoms"-.

Anthracene-magnesium and its 9,10-bis<trimethylsilyl) derivative react with organoaluminium compounds in a number of different ways (Scheme 3). The magnesiunrp-<Q,lO-dihydro-Q,lO-anthrylene)- aluminate complexes ( 8 ) , (9) and (10) are formed in the reaction

of anthracene-magnesium with trimethyl- and triethylaluminium in toluene or with BtZAlOEt in thf. The disilyl derivative, in

contrast, react6 with trimethylaluminium to give the 1:2 adduct (11). Reaction of ( 8 ) with MeAIClz affords (12) or its thf

64 Organometailic Chemistry

Scheme 3


IIeSSi .Ilea

EtnAlC1 1 t (nt2) I l e ~ A l -

-&aAl tTHF

(11)

2BteAlC1

tBtnAlC1 - - E t s A l . THF

.si&20 1 THF \A(””

Scheme 3 ( c o n t . 1


cp2z:ef-0 t R ' z A l X cp22r-0 \ \

b \ \ b 0 -2rcp

Zr -X R

R C H 2 C ( C L ) a R' = We, Bt X = C1, H, We

cp2Zr-0 x cp2Zr \ - 0 jigR'

R Y / \)R.

(15)

Scheme 4


50psi

45' t co-

Schelpe 5

68

He2


He2

(19)

GalIea t BaGaHI l/n[ 1 I a ~ G a H l n

Schem 6


adduct. With BtaAlCl, depending on the molar ratio, the disilyl derivative gives either the chloromagneoium-aluminate (13) or the monomeric ethylaluminium compound (14). X-ray analyses of (10) and the thf adduct of (12) show that the metal atoms occupy axial positions in the 9,10-dihydro-9,10-anthrylene groupa1. Treatment of the zirconocene ketene complexes tcp~tZr(0CCHR)Ir with a variety of alkylaluminium reagents affords the complexes (15) (Scheme 4>.The structures of four of the complexes have been determined and show several features in common. The two zirconocene keteme monomers are spanned by symmetric dialkylaluminium and hydride, chloride or methyl bridges to form slightly puckered six-membered rings. Reaction of the methyl derivative (16) with acetylene produces the zirconocene cyclic enolate <17), whilst with carbon monoxide the zirconocene acyl-enol complex (18) is formed (Scheme 5)"". The complex 1 ( ~ ~ P > ~ B I < M ~ ~ P C H ~ ) = A ~ ( C H ~ P H ~ ~ ) I S is formed in the reaction of the cyclic phosphinoaluminium compound (19) with IOI<COD>Z in the presence of trimethylphosphine. In solution the complex I s in equilibrium with (Me=P)dl and CBiC (Me2PCHz> %A1 (CH2PMer;e) =I 1) (x unknown)

Dimethylgallane is best prepared by the reaction of trimethylgallane with BaGaH. at ZOO, and is a viscous, colourless liquid <map. ca. 0'; v.p. at 20' ca. 1 torr). The dimeric structure ( 2 0 ) was confirmed by an electron diffraction study, and several of its reactions are shown in Scheme 6"*. Other gallium structures of note are the two bis~trimethylsilyl~arsinogallanes, C <Me~SiCHp)oAsGaPhrl~, which has a planar central four-membered CGa~Aszl ringae, and the cluster shown in Figure 1 which contains a central CAs7GasI core"', and several complexes of tridentate pyrazolylgallate ligand~~'-~~. The eilylmethylindium compound COC(Me~Si)~CIn)r(OH)cl has the unusual cage structure depicted in Figure 2 in which the central oxygen atom is bonded to all four indium atom situated at the corners of a tetrahedrona1. The reactionm of indium<III) chloride with indium(1) halides in a dichl oromthane/ to1 uene / B, B, B' , B' -tetramethylenedi amlne mixture yields bisctmen) adducts of the methylene-bridged di-Indium compounds, Cl<X)InCH=InCls. Structures of the complexes with X = C1 and Br have an average In-C-In bond angle of 117.6'43.

Intensely coloured charge-transfer complexes are formed from HOnX, (X = Al, Ga, T1; X = C1 F) and benzene or nethyl- substituted ben~ene8*~. The unucual aluminium bis(dicarbol1ide)


Figure 1. The structure of f (PhAsK) (&Ga) (PhA6)s(IGa)*l (R = ICeoSiCHr) (reproduced from ref. 36).

Figure 2. The structure of f O ~ ( ~ ~ S l ) ~ C f n ) ~ ( O ~ ~ ~ l (reproduced from ref. 42).

Group III: Aluminium, Gallium. Indium and Thallium 71

ehown in Figure 3. has been obtained by the CO-catalysed conversion from closo-3-CaHr-3,1,2-AlCo~H1~. faces of the two dicarbollide ligands are nearly parallel, and are coordinated in a penta-hapto fashion to the sanm alumlniun atom. In addition, a diethylalumlnium moiety Is bound to one of the dicarbollide cagee via two B-H-A1 bridges*s. %-Bonding of this type is highly unusual for alumlnium(III), and is more commonly observed in the heavier elements of the Group in their lower oxidation states, and the structures of mure examplee have been described. Those of X n ( C d t e ~ ) * ~ and Tl<Cdes)r7 are quite different. The yellow orange indium derivative crystallizes in hexameric clusters, with the indium atoms arranged in an octahedron on the exterior of which are the C d e c ~ group. That the compound is relatively volatile suggests that the octahedral clusters posaass only marginal stability, with monomeric species probably formed in the gas phase*=. other hand forms a polymeric zig-zag chain structure similar to that of TlCdL, but with much shorter T1-T1 distance6 indicative of a much higher degree of covalent bondine4’. The structures of two arene complexes, one of gallium and one of thallium, have been reported. Cooling a mesitylene solution of TlOTeFc gives crystals of C TlOTeFr <mes)d P. mes, which contains a central t TlaO~tl ring. The coordination sphere around each thallium atom 1 6 pseudotetrahedral with the two oxygen atoms from two bridging teflate groups and two hexahapto mesitylene molecules, although the T1-C distances vary over a range of values4’. C2.23Paracyclophane forms 1:l complexes with GaZClr and GaZBrr. in benzene at ambient temperature. The complexes are in6OlUble in common organic solvents, and an X-ray study of the bronm derivative shows it to comprise an intricate highly symmetrical three-dimensional lattice network. Each gallium(1) centre I s

complexed by two C2.23paracyclophane molecules, Whose parallel pairs of aromatics rings are tilted relative to each other by 56.7’. The 1:l 6toichiometry implies that each paracyclophane is bonded in turn to two Ga<I) atoms which are Situated nearly centrically above each of the arene rings. The polydecker Chain6 of alternating gallium<I) ions and paracyclophane molecules thus formed are cross-linked by tetrahedral GaBrd- anions, each of which provides one bromine atom to bridge two gallium<I) centres*m.

The two planar

The thallium analogue on the


Figure 3. The structure of conrao-3,3'-Alt (exo-B,S-(p-H)2Al (C2&)2-3,1,2- AlCrr&H-) (3' , 1' ,2'-Al (CnBdi11 ) I (reproduced by permheion from J . Am. Chen. Soc. 1986, LpB, 5367).

<cH2\ q7-A T 1

(21) (22)

.,+ + F-CHO IIenAlC1

B' R3 R4

Scheme 7


Reaction of thallium(1) ethoxide with dicyclopenta- dienylmethane or dihydrofulvalene gives the new thalliumCI) reagents, bis<cyclopentadienylthallium)methane (2l)Oo and fulvalenedithallium (22)01, both of which are useful synthetic reagents for the preparation of transition metal complexes.

Indium<III) porphyrins having an axially-bonded perfluoroaryl group, syntheslsed from the appropriate Grignard raegent and the chloroindium porphyrin, are quite stable thus enabling the electrochemical behaviour to be readily studied. Such complexes can be oxidized or reduced by multiple single- electron transfers. Two reversible reductions were observed in non-aqueous media and corresponded to ring-centred reaction8, the first of which generates a stable C (P)In<CeF4X)ln' radical anion. The complexes can also be oxidi8ed by two one-electron abstractions, but unlike the previously described tr-bonded alykl- or arylindium porphyrins, no cleavage of the cr-bond occurred following the first oxidationm2.

The thermal stability of diethylalane is decreased in the presence of triethylamine, (Me&H>=O and <He&HO)rTi. The basic reaction is disproportionation giving triethylaluminium, hydrogen, aluminium and ethane. In the presence of triethylamine, the decomposition of diethylalane proceed8 at a rate eight times faster than does diis~butylalane~~. Gel permeation chromatography has shown that the hydrolysis products of triethylaluminium at a molar ratio of 2:l <EtoAl:HaO) comprise a mixture of ethyloligoaluminoxanes, a tetraethyldialuminoxane trimer and trlethylaluminium. Isolated pure tetraethyldialuminowne trimer does not undergo further separation and is stable at r o o m temperature for several weeksm4. The 1:l reaction of triethylaluminium with methanol gives dimeric and trimeric IEt;cAlONel together with a tetranuclear complex formed from two moles of EtdlOEt and two moles of EtAl(0Me)a and containing six- coordinated aluminium. The 1:l methanolysis of EtaAlPhCB gave 91.3% of the dimer, along with small amounts of the trimer. In the presence of pyridine, EtdlOEt undergoes a dieproportionation to EtoAl. pyridine and I BtAl <OHe)=l dmm. The alcoholysis of tetraethylaluminoxane in a 1:l molar ratio proceeds at


(i): MeaAl , c p 2 Z r C l a ; <Ill E l + <H=O, DzO, BBS, BCS, A c C l ) B1 = H, I), B r , C 1 , A c

Scheme 8

T l C 1 3 + 13eC<: 0)CH;cR ____) C l n T l C H z C ( : O>CHr;cR

1 / 3 T 1 C 1 3 .1 HeC ( : 0) CHClR

Scheme 9

.$- L1aPdCl.i THF or BkO; 25'

Ar

S c h e m e 10

R ArTl COCOCFa) 2 t


temperatures in the range -60'- -35' to give triethylalkoxy- alumoxanes, C Eta (RO)AlnOlh and ethane"". Trimethyl- and triethylalumlnium undergo 1,2-, 1,4- and 1,6-addition to 2,4,6- tri-t-butylnltrosobenzene to give after hydrolysis the corresponding nitrones and oximes. triethylaluminlum the addition products partly undergo further reduction to aromatic amines bearing an ethyl group on the

nitrogen atom or the rings7. formation of 1:2 complexation between esters and trialkylalanes-e.

In systems containing

Bo evidence has been found for the

Organoaluminium reagents prepared from RCECCHZBr in ether react with acetals to give selectively a-allenic etheISR*, eg:

(1) Al/ether RCr CCHr Br * CH==C=C (R) CH (OR" ) R'

(2) R' CH (OR") ;i:

Tri-cis-myrtanylaluminium can effect the enantioselective reduction of prochiral ketonesGc'. Dimethylchloroaluminium

catalyses the condensation of silyl enol ethers and aldehydes at -78' in dlchloromethane giving j3-trlmethylsiloxyketones (Scheme

7>61. Irradiation of the AlEtClr: complex of endo- tricycloC 5.2.1. 0 2 a =I deca-4,8-dien-3-one yields the AlEtCls complex of exo-tricycloC 5.3.0. Oz.sl deca-4, 8-dien-3-oneG2. Carbometallatlon of 1,4-bis<trimethylsilyl)-l, 3-butadiyne with

trimethylaluminium in the presence of cpzZrC1= catalyst selectively produces an alkenylaluminium intermediate which, on treatment with water and various electrophiles, affords 2-methyl-

1,4-bis(trimethyls l lyl)- l -buten-3-yne and it6 1-substituted

derivatives <Scheme 8Iey. The TiClA-BtpAlCl catalyst system induce6 endo-C2+23 cycloaddition of bis(trimethylsily1)acetylene to norbornadienefiA.

The room temperature reaction of simple aliphatic ketones with an aqueous solution of thallium(II1) chloride leads to the formation of the mono-oxoa1ky1thal1ium<III) derivatives (23) which are then converted to selectively monochlorinated a- monochlorinated ketones (Scheme Q > Q c . Methyl vinyl ketone is 13- arylated by arylthalllum compounds in a reaction which is catalysed by lithium tetrachloropalladate <Scheme The thallation of anilides with thalllum(II1) trifluoroacetate in a mixture of trifluoroacetic acid and ether affords the ortho- thallated derivatives <24), which yield 2-acetamidotolanes on reaction with copper<I> phenylacetylide in acetonitriles7. Ortho-

76 Organometaliic Chemistry

Scheme 11

*Bu

TPPAlEt t "Bu- -CII=C& TPPA1-Ckt!=CIi-Ctia-Bt 6

Scheae 12

R" G C H

.* / cl'A1llas

cp2Zr AR 0 t AlNeo + cpAr- x,,,,3 \ c1 'Cl'

A


thallated anilides also undergo facile photolysis in cyclohexane suspension forming benzoxazoles (Scheme ll)=-.

The Al-C bond of ethyl tetraphenylporphyrinatoalumlnium <Al(TPP)Bt) undergoes addition of the A1-C bond to t-butylvinyl ketone via an enolate aluminium porphyrin intermediate (Scheme 12)**. That the reaction is accelerated tremendously on irradiation by visible light is understandable since it has been demonstrated that the A1-C bond of Al<TPP)(Bt) is horwlytically cleaved upon irradiation by visible light in benzene in the presence of an excees of 2,4,6-tri-t-butylnitronitrosobenr, yielding spin adducts of Al(TPP) and ethylradicals with a quantum yield of the order of lo-" 7 0 . The insertion of sulphur dioxide into the gallium-carbon bond of gallium(III> porphyrins CGa(Por)RJ gives rise to sulphinato gallium porphyrins which are easily oxidised to the corresponding sulphonato complexes71.

Treatment of the acylzirconium complexes cpaZr(C1)COR with trimethyl- or triethylaluminium at 0' in an aromatic eolvent affords the ketone complexes (25) in high yield. These complexes react cleanly with acetylenes, ethylene and ketones in reactions that promise to be of considerable synthetic utility (Scheme 13)". Wolybdenum-aluminium complexes derived from MoO&l= or MoOCl=(thf)= and trimethylaluminium have been shown to exhibit carbonyl alkenating capacity. These reagents, for which the structures (26) and (27) were assumed. A tungsten complex analogous to (27) was obtained from WClr<thf)s, and was also active. Conversions from the carbonyl compound to alkene were high; for example, benzaldehyde to styrene conversion could be accomplished in 98% yield7=.

1.

2.

3. 4.

5.

6. 7 .

8.

References

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81 Group III: Aluminium, Gallium, Indium and Thallium

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'Comparison of the structure of 9,10-dlhydro-9,10-anthrylene COmpOUndS of magnesium and alkylalumlnlum' , H. Lehmkuhl, A. Shakoor, K. Hehler, C. Krueger and Y.H. Tsay, Z.. T a i l B, 19851 4 p B S 1504.

'Hew property of organomtalllc compounds - redox- chemiluminescence from Interaction with xenon dlfluorlde and molecular oxygen' R.G. Bulgakov, G. Ya. Malstrenko, V.B. Yakovlev, S.P. Kuleshov, G.A. Tolstlkov and V.P. Kazakov, Dokl. -, 1985' 282, 1385.

'Structure of phosphorue organlc compounds. Part XXXII. X-ray structural etudy of 1,3-bls(l-1mthylsllyl)-2- bls(trlmethylsllyl)a~no-214,4-trlphenyl-l13,2,4- dlazaphosphaaluminamthldlne and 2-bls~trimethylsllyl)amino-3- tert-butyl-2,4,4-trlphenyl-l, 3,2,4- thlaazaphospbaaluninamethidine' A. B. Chernega, 1. Yu. Antlpln, Yu.T. Struchkov, I.B. Blldeskul, V.F. Shul'gln and V.D. Romanenko, Zh.. Khim., 1985, 28, 120.


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'Determination of the kinetic-equilibrium parameters of the reaction of triphenylaluminium with benzophenone' , B. Palm, and V. Palm, U A a , 1985, 22, 131; C h e m . B b e , 1986, U, 6544p.

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'Thermal decomposition of chloroalkyls of aluminium, gallium, and indium as sources for producing thin dielectric films', B.A. Sysoeva, B.D. Bovikova and 0.1. Mittov, F i z - u - , 1984, 117; m-,, 1986, m, 148957d. 'Fixation and activation of carbon dioxide on aluminium porphyrin. Catalytic formation of carbamic ester from carbon dioxide, amine and epoxide', F. Kojima, T. Aida and S. Inoue, -, 1986, LpB, 391.

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6 Group IV: The Silicon Group

BY D. A. ARMITAGE

BY 0.A.ARMITAGE

1 l r i t r o d u c t i o n

I n v iew o f t h e v e r y e x t e n s i v e range o f reviews, t h e s e a r e covered by conimon

p u b l i c a t i o n source. Review a r t i c l e s on organos i L icor i c h e m i s t r y cover s i Ly l -

cyclopropanes as v e r s a t i l e s y n t h e t i c reagents, v i n y l - and a l k y r i y l s i l a n e

t e r m i n a t e d c y c l i s a t i o n reac t ions , and t h e f o r m a t i o n o f y l i d e s b y d e s i l y l a t i o n

o f onium s a l t s , whi l e t h e f l u x i o n a l i t y o f q l - c y c l o p e n t a d i e n y t ma in g roup

compounds i n c l u d e s S i t o Pb.' The use o f 3 -ch to rop ropy t t r i a t koxys i lanes as key

i n t e r m e d i a t e s f o r t h e commercial p r o d u c t i o n o f f u n c t i o n a l i s e d s i lanes and

p o l y s i l o x a n e s i s reviewed,< and a wide range o f a r t i c l e s on o r g a n o s i l i c o n arid

b i o o r y a n o s i li con c h e m i s t r y pus t i shed i n c l u d e mult i p l y bonded d e r i v a t i v e s ,

s h o r t - l i v e d in te rmed ia tes , p o l y s i lanes and p o l y s i L y l a t e d compounds, c a t a l y s i s

o f h y d r o s i l a t i o n , S i coinpounds i n o r g a n i c s y n t h e s i s - use and r e a c t i v i t y ,

h i g h l y h i n d e r e d o r g a n o s i L i c o n compounds, o rganos i L i c o n p o l y m e r s u p p o r t e d meta l

c a t a l y s i s , and t r a n s i t i o n m e t a l - s i L i c o n and germanium ~ h e m i s t r y . ~ A s i m i t a r

range o f a r t i c l e s c o v e r i n g S i i n o r g a n i c s y n t h e s i s and b i o s y n t h e s i s were a l s o

p ~ b l i s h e d , ~ a l o n g w i t h i o r r m o l e c u l e r e a c t i o n s i n v o l a t i Le siLanes, s t r u c t u r a l

chemis t ry o f S i , m o l e c u l a r and e l e c t r o n i c s t r u c t u r e o f 5- and 6-coord ina ted S i

compounds, and s y n t h e t i c aspec ts o f t h e c h e m i s t r y o f s i l y l t h i a z o l e s ano

o x a ~ o l e s . ~ N u c l e o p h i l i c s u b s t i t u t i o n a t S i i s compared w i t h t h a t a t P, and

e l i m i n a t i o n a d d i t i o n mechanisms s i m i l a r l y compared. T h e r o l e of S i , tie, and S n

i n t e r m e d i a t e s i n t h e p r e p a r a t i o n o f m u l t i p l y bonded phosphonium compounds i s

reviewed.' E x t e n s i v e surveys cover i n o r g a n i c s i ly lenes, (R C ) 1.1, s i lcnes, t h e

X-bonding t o ma in g roup elements, s y n t h e s i s and r e a c t i v i t y o f t h e h e a v i e r

group I V (and V ) e l e ~ e n t s , ~ a n t i t u n o u r and t o x i c e f f e c t s o f Si, Ge, Sn, and Pb

compounds, w i t h s y n t h e s i s o f Ge a n d S n ones, Ge compounds i n b i o l o g i c a l

systems, >Ge=X species, and t h e m o l e c u l a r s t r u c t u r e o f s i Latranes,' a l l y l t i n

compounds i n s y n t h e s i s and t h e c o n t r o l l e d r e l e a s e o f o r g a n o t i n reagents,

5 5 2

84 [For references see page 119

Group IV: The Silicon Group 85

o r 5 a n o t i n d e r i v a t i v e s o f sugars, W4R o f s i l y l a c e t y l e n e s and t h e r e a c t i v i t y o f

S i s y n t h e t i c intermediate^.^ Comparat ive S i g roup rev iews i n c l u d e organomet-

a l l i c s i n synthesis, t h e rearrangement o f oryano-heavy m e t a l azides, c y c l o t r i -

s i lanes, germanes, and stannanes, and M-M‘ bond Length data,” whi 1s r e v i e u s

i n o r g a n o t i n c h e m i s t r y cover m e t a l c a t a l y s i s , n o t a b l y Pd cross-coupl ing, use

i n o r g a n i c syn thes is , and ’I9Sn nmr parameters.

Persona l r e c o l l e c t i o n s cover s i l y l c a r b i n o l s t o s i l a r t h y l e n e s , S i - H t o C-H

a c t i v a t i o n , and p o l y s i lane h i g h polymers,12 annual rev iews t h e S i - C Sond (19B3

a n d 19841, s i l a f u n c t i o n a l compounds (19841, and l e a d (1Yt33),13 w h i l e a monograph c o v e r s o r g a n o s i L i c o n c h e m i s t r y , t u o v o l u m e s o f G m e l i n s i l i c o n

c a r b i d e and R3SnO- (R=Pr, Bun) compounds, and Chapman and H a l l source books,

o r g a n o r n e t a l l i c compounds o f S i and Ce th rough Pb.I4 Organometa l l i c S y n t h e s i s

i n c l u d e s 50 o r g a n o s i l i c o n g r o u p cOmpOlJnds, h a l f o f k h i c h a r e v a r i o u s l y

s u b s t i t u t e d s i ldnes and p o l y s i l a n e ~ , ’ ~ ~ I n o r g a n i c S y n t h e s i s i r i c ludes I?e3SiClizH

(M=Al,ln) d e r i v a t i v e s , (Me3SiNH)ZC0, Ph(Me3Si)C=PC1, C(fle3Si) GI PCl and

Ph S r ~ t r r ~ , ” ~ w h i l e u r y d n i c S y n t h e s i s t h e p r e p a r a t i o n o f (f.?eL:iI3S Fle2SiF from

fle.SillMe2 and SF4, arid (€)-3-Me-SiCH=C~ICH~Grt from p r o p a r g y l a l c o h o l s .

T h e r e a r e a L i a i t e d number o f r e l e v a n t r e v i e w s i n t h e Japanese,’6a

Polish,16‘ and R u s s i a n L i te ra tu re .16c T h i s d r t i c l e c o n t a i n s 1203 re fe rences .

11

+2 * - 2 152 3 5

2 The Carbon-fSetalLoid Bond

C a l c u l a t i o n s i n d i c a t e t h a t a d d i t i o n o f t i t o H,C=SiH2 i s more exo thermic a t C

t h a n a t S i b u t t h a t t h e a c t i v a t i o n energy i s g rea ter , and s i l e n e s ( i r r a d i a t i o n

of ?c,s i 2, A n a x 255-293nm) undergo a s i g n l a t r o p i c C1,3I-hydro~en migra t ion ,

and add a l k o x y s i Lanes s t e r e o s p e c i f i c a l l y th rough ~ y r r a d d i t i o n . ’ ~ Heatinc;

dut2Si FCLi (SiMe 1 y i v e s tle.Si=C(SincS)SiMeUut2 2 th rough rear rdngcncnt . I t

undergoes r a p i d m e t h y l m i g r a t i o n and C2+23 and C2+41 c y c l o a d d i t ion,I8 whi l e

Ile Si=C(SiMe3)Z and i s o p r e n e g i v e p r e d o m i n a n t l y t h e C2+41 cyc loadduct w i t h S i

add ing a t t h e inore h i n d e r e d end o f t h e dicne. Wi th t rans-p ipery lene, tht .

I - s i la-5-mcthylcyctolirx-3-cne i s formed almost e x c l u s i v e l y . The adduct

~e2Si=C(SiPie~)*.N:‘lej i s s u f f i c i e n t l y s t a b l e a t O°C t o p r o v i d e a convenient

source o f t h e s i lene, which d i m e r i s e s even a t -lU(?‘C, ani; forms cyc loadducts

and ene d e r i v a t i v e s . ” The gerracne t‘ie2Ge=C(SiMe3)2 i s formed s i n l i l a r l y and

g i v e s a s t a b l e cyc loadduct w i t h bentophenone. X-i?onc! s t r e n g t h s have been

c a l c u l a t p d f o r C=C(h4-6Xkcal),C=Si (3S-bkcal),C=Ge(3lkcal) and C=Sn(lqkcal) .2c

3 2

2

The heat o f f o r m a t i o n of : S i K 2 i s calcu1atc.d as h923kca l w i t h i t s D r o t o n

a f f i n i t y ?I) lL3kcal . The k i n e t i c s of h y d r o g e n a t i o n of : S i A > a l s o Supports t h e


fo rmer f i g u r e , S i t i , decompos i t ion i n t h e presence o f o l e f i n s proceeds t h r o u g h

:SiH2, w h i l e E A fo: : S i H 2 a d d i n g 1,4- t o s-G-buta-1,S-dienz i s o n l y 4kcat."

A h I n i t i o s t u d i e s show p r o t o n a t i o n of S i c 2 t o g i v e L i n e a r SiCCtI ' , t h e I t 5 - u i -

s i LabicycLoC1.1.03but-2-ene :wa: t o be more s t a b l e t h a n :Si=C=C=Si:, and

s i n g l e t s iLacyclo,>ropenyLidene t o be t h e most s t a b l e o f t h e 15 isomers o f

C S i l l 2 , u i t h :izC=C=Si: 17kcat and :SitiC=CH 22kca l higher.22 C a l c u l a t i o n s

c o n f i r m t h e 45iinm a b s o r p t i o n a s due t o g r o u n d s t a t e t :e2Si: w i t h 43i:rirn

i r r a d i a t i o n c o n v e r t i n g i t t o I -methy ls i tene, u h i t e k i n e t i c s o f t h e reverse

react ion, e s t i m a t e d t h r o u g h buta-1,3-diene adducts, g i v e t h e a c t i v a t i o n

er i tha lpy o f 26.9+11.7kcaL.moLs-' .23 Redct ions of MeZSi=CH2 w i t h an ions

e s t a b l i s h e d t h e p o l a r i t y o f t h e S i = C doub le bond ana i t i s thought t o have an

a c i d i t y c l o s e t o t h a t o f ~ e O k i . ~ ~ d - S i L y t s i t y t e n e s rear range th rough d i s i l e n e

in te r ined ia tes , w h i l e bond e n e r g i e s f o r s i n g l e and f o r double bonds t o C and t o

S i a r e compared.25 Ne S i : adds t o 3,3,6,6-Mt-4-1-S-cyctohe~~t-4-yne t o g i v e t h e

s i Lirerle, u n l i k e o t h e r ace ty te r ies which form d i s i t a c y c t o h e x a d i e n e s i f

unhindered. S i t y l e n e s NePhSi : y e n e r a t e d f rom t h e 7 - s i labenzonorbornadienes

r e a c t w i t h 9,lO-dime t hy L an t l i racene t o y i e L C t h e 7 - s i Ladibenzobi cyc LoCZ. 2.13-

hcpta-2,5-diene, whi Le I r k S i : g i v e s a s m a l l amount of t h e dis iLabicyctoC2.2.21

octd-2,5-diene ( f rom Me2Si=Sii4e,). H iyhLy h i n d e r e d s i l y t e n e s yenera ted f r o m

t h e dibenzoC2.2.13 hepta-2,S-di ene (whi ch i soltie r i ses t (3 t h e 2,3,6,7-dibenzo-

C3.Z.Olheptadiene) r e a d i t y d i m e r i s e t o t h e d i s i Ler~c, whi L e Mes,Si: adds t o

a t l e n e s t o g i v e s i Lacyclopropenes which underyo 1 , 3 - ~ r o t o n m i y r a t i o n s on

p h o t o t y s i s t o g i b e the 2-s i t r l lutd-1,3-dienc.2h Conformat ionat d i s t o r t i o n s i n

But S i f ragrnents have been anatysen, u h i t e t h e molar excess thcrinooynamic

q u a n t i t i e s f o r 4 g l o b u l a r stannanes i14Sn w i t h t rans-deca l in , a heptanethy t -

nonane and t r i m e t h y l p e n t a n f shows a s t e r i c c o n t r i b u t i o n .

Me3SiCH2ii c r y s t a t t i s e s as hexamers w i t h 2 d i s t i n c t L i - - -L i d i s t a n c e s o f

246 and Jlapm. U i t h Pie C (Ph,P)2hCt2, Me,SiCH L i g i v e s t h e ~ - m e t a L L a t e d 5 5 J . , 2

complex Pie C R h ( C ii PPh2)Cti2Sir4e3, b u t Kc.SiCti kyCL, W,C RhCL(PPh,)CHZSiilc3.

(I'le.,SiCH2)2ilg a t k y t a t e s 14 (r-02Ct4e)4CL2 (M=t?u,us) and f k R u X , ( X = C L o r OSiile.,)

t o g i v e niono and b i n u c t c a r s i LyLnethyL d e r i v a t i v e s . The coriiptexcs

(iie C 1 Ln(CkizSiAe.J)ZLi (3ME13 (Ln=Pr,Lil) have been prepared, t h e r e a c t i o n s o f

( C 5 1 i , R ) .,Y (Ci12SiRe.,)TliF, l,?-V. ( C I i Si l le - 1 , ( :JTlc2)4 and iSOs(CH S iMe3)4 studied, 29 and (Ke.SiCH2)LZr(Xe PCti CI! PKe2) shown t o e x h i b i t Zr - - -d -H i n t e r a c t i o n s .

The carhen9 complexes (COI5W=CGJP )SiPh3 undergo 2 - m e t a t t a t i o n o f t h e phenyt

g r o u p (U-Car 3:11.4pm) o n + e a t t r i g w i t h CO tcss , w h i t e R 2 S 2 c a t a l y s e s t h e

dea LcohoLysi s of ( C o ) 5W=C (0Et)S i Ph9 by R'SH, g i v i ncj n o t a b l y (C0)5W=C(SR)S i Phj

th rough a h - c e n t r e t r a n s i t i o n state.30

2

2

2

L

2

27

5 5 6 4 5 2 ' 5 - 2

2 7 2

5 5 2 2

4 - 2 2 5 L 2

I 4 2 2 2

' 2


1.3-u i - t - o u t y t-2,4-bi s ( t r i methy l s i Ly L)-I ,+di boracyc Lo l ju tad i ene d i a n i on

occurs as a dimer o f square a n t i p r i s m s t r u c t i ; r e w i t h L i lc i r iuging t h e 4 p a i r s

o f C atoms between t h e t h o squares. The l,3-(t'ri7ii) i i c r i v a t i v t . i s monomeric

w i t h a r i n g p u c k e r i n g ang le o f 32.2' and undergoes C-C s i t y l m i g r a t i o n on

comptexing d i t h gold." --(11P,Si)ZC2Dl,!iL; can be w s i t y t a t e c i u i t h F- o r HCL

t o Give e - M e 3 S i C 2 B 4 t i 7 ana t h e s t ruc tccrus o f s e v e r a l s i t y tcarbordr les a r e

c-lctcrinined. They rcciuce altienydcls and ke tones t o 1' aiid The

ctoso-star indc' j rboranc Sn(fAe,Si),C,,j!+ii4 conptexes a t t i n w i t h b i p y r i d y t , . whi l c

(I'ie-,Sil7C t ' 1 1 and GeCtL y i v e s t l i e gcrlnanocenr C( i le,Si)2C k3 i i 3 iie 5 s w e l t a s

t h e Ge(I1) d c r i v a t i v e ctoso-C(r:e-Si) C E H4lGe. The analogous s i l i c o n

d e r i v . 3 t i v e s r e s u l t f r o n s i c t 4 and :la+Li+(rle3Si)2CgFii;:142-, u h ~ , t c

~ i ~ - ~ - 7 , ~ - ~ ~ r j ~ t i ~ , and s i c t 4 givi: t h e t i s - t t5 -c i i carbo t t i c :e s i satljwictl.'2

Me3SiC[J s i t y l a t e s a lcoho ls , phenols, c a r b o x y t i c acids, amines arid t h i o t s ,

g i v e s p - s u b s t i t u t e d d-(Pie S i 0 ) a c r y t o n i t r i l c s ( f r o a i s o m e r i s a t i o n o f adducts o f

Me-SiCr i and d , p - u n s a t u r 3 t ~ d a t d s h y d e s ) w h i c h l j i v e s a n b i d e n t a n i o n s t h a t

ine thy la te OL t o g i v e a,/3-uiisdtl irdte!J IiiEthyL ketones.3' S i t y t cyanohydr ins

r c s l r t t f rom >C=O, Iie,SiCL, snd Lit?;, w h i t e C i i - i n i t i a t e s a d d i t i o n o f ChF5SiAr..

t o a c u t o p h e n ~ n c s , ~ ~ i n 6 o p o x i d x arc' opened by .i .S iC id /Zn12. F l u o r o t r i n i t r o -

benzenes a r e s u h s t i t u t e d ,jt F by Me3SiCii, C-pheny ln i t rones add Ilc SiCi . ; t o G i v e

t h e cyano-G-l:,e-,.SihydroxyLamine u h i c h regenera tes t h e n i t r o n e w i t h AgF, and

n i t roa l k e n r s a r: subs t i tutec: by Me$ i C f l t o g i v e s u b s t i tu tec i a 1 l y tn i t r i Les.j7

Pd c a t a l y s e s t h e a d d i t i o n o f r4e3SiCtll t o a c e t y l e n e s ( g i v i n y p y r r o l e s ) , a l l c r i e s

( t o g i v e a t l y t n i t r i l e s ) and t h e s u b s t i t u t i o n o f a r y l hal ides.38

T r i m e t h y t s i l y t m e t h y t i s o c y a n i d e Me S i C H p C , bp 86°C/105min can be

convenient t y p repared from Me S i C H . C L and FJatll:CHO, f o l l o w e d b y d e h y d r a t i o n

u s i n y POC13/Pri,!41~, and avo ids u s i n g f.lcriC.39 Me,SiC(Li)N., Gives a c y l s i lanes

u s i n g RX/i lCPBA,L1,2,~-thiddiazol~s w i t h R C ( S ) X 4C2=Ne0,i4ei), and w i t h ( B u ~ C ) ~ '

g i v ? s t h e c y c l o p r o p c n y t d e r i v a t i v e which dimerises, remarkably t o t h e 1,2,4,5-

t e t r a a z s t ~ r ? n z e n e . ~ ~ The phosphinocarbene genera ted f r o o (Pri21,4)2PC(N2)Si:.le3

r e a c t s u i t h HCUCL t o y i v e (Pri2N)f(0)C3CR, Me-SiCti2N=CR2, p repared f rom R C O /

Ph,P/Ke SiCH.li.. p r o v i d e s a 2 - a z a a l l y t a n i o n ~ y n t h o n , ~ ' azomethine y l i d e s g i v e

h e t e r o c y c l e s t h r o u g h 1 , 3 - ~ y c l o a d d i t i o n . ~ ~ H S i C L - adds t o enamines, amino-

met hy t stannanes g i ve R2N CH2COR ' w i t h R ' CO C I, 2-stanny tmet hy l p ropenam i des g i v e

@-methyLene-8-butyrolactones w i t h RCIIO, whi Le (PhC:J)2?dCl c leaves t h e Sn-C

bond o f R3Sn(CIi. ) NMe2 t o g i v e 8-aminopropylPd che la tes . F - S i l y l f - y l i d e s 2 3 w i t h e l e c t r o n e g a t i v e s u b s t i t u e n t s on t h e s i t y l group add s u b s t i t u t e d aldehydes

w i t h h i g h d i a s t e reose lec t i v i ty.44

I_ 2

.J - - - 2 L 2 ' 4 5 .> 2 4 4 2

5 2 2 4

3

J

36 I

3

3

3 2

5 2

4 3 L . ,

3

4 3

Me2Si (CH2PPh2I2 and r'leZSi (v iny1)X (X=CH2PPh2, CHzfdMe2 and CH2Srie) have been


used as b i d e n t a t e Ligands and PleSi(CH2Plle2)3 as a t r i d e n t a t e l i g a n d t o t h e

?$c6lI6Fe r e s i d u e which g i v e s a d i - i r o n p - v i n y l i d e n e complex on r e d u c t i o n i n

t h e presence of C2I l4 . The phosphines But

cyc Lometa L Lated h y d r i ties w i t h (C:,H1 4)41r2CL23:43 [mil (PPh2I2J2 (M=Ge,S n,Pb)

show dynamic b e h a v i o u r i n s o l u t i o n a n d a C-d-bonded a n d P,P-cora ina ted

h i d e n t a t e Ligands i n t h e s o l i d s ta te , i n c o n t r a s t t o SnCC(PMe2)2X12 (X=PFlleZ,

SiFie3), which i s excLus iveLy P-bonded i n t h e These tin(11) Ligands

r c a d i Ly g i v e s t a n n y L e n e c o m p l e x e s w i t h g r o u p V I m e t a l c a r b o n y l s . N h i Le

CLZSnl/(C0)5 and _o-Ph2PC6H4Li g i v e t h e phosphino s t a b i L i s e d s tanny lene conplex,

a t tempts t o make t h e p a r e n t s t a n n y l e n e g i v e s t h e mixed o x i d s t i o n s t a t e t i n

compound (pPh2bCH C t i ) Sn<--+Slf;CL s t a b i l i s e c l by t r i p l e PhZP c ~ o r d i n a t i o n . ~ ~

(Me3SiCH2)2AsH and Ph Ga g i v e t h e b r i d g e d d imer whi l e (Ile3SiCH2)3Ga and PhAsHZ

y i e l d an As7Ga5 cage.

aC ,p-r lnsaturated s i LyL ketones p h o t o t y s s t h r o u g h v a r i o u s n i i s rd t ions , F-

i nauces p h e n y l m i g r a t i o n i n PhileZSiCOMe t o g i v e (MezSiO) and CH3CH(Fh)OH,

d h i L e oL-WejSi k e t o n e s c a n be d c s i l y l a t e d b y Ur2, Ph lCL dnd PhSeUr.49

CycLopropyL s i LyL ke tones r e s u l t from d - L i t h i o c y c l o p r o p y l s i Lane and C12CHOHe,

f rom g e r a n i o t d e r i v a t i v e s u s i n g fle7Si-, and a r e r i n g opened o r r i n g expanded

( t o d i h y d r o f u r a n s ) b y a c i d . 5 " Ordomo- and c h l o r o m e t h y t k e t o n e s f o r m f r o m

s i l y l m e t h y l ke tones r i t h Br2 i n C C L 4 o r S O z C L z i n CH2CL2, m a n t i o n e r i c a l l y

pure p - s i L y l c a r b o x y l d e r i v a t i v e s by asymmetr ic 1,4-addition t o PI-enoytsultdnis,

w h i l e HgCII) induces t r a n s m e t h y t a t i o n o f I!e3SiC1i2C02 and f-le3Si (Ck12)3S33 . O p t i c a l l y a c t i v e p - s i l y l a c e t i c a c i d and s i Lylmethylamines have been made t o

de termine c h i r a t amines and a c i d s r e s p e c t i v e l y , o f - s i l y L e s t e r s and PhCHO used

i n c ross aLdoL c o n d e n s a t i o n w i t h moderate s t e r e o s e l e c t i v i t y , whi Le

S&t l ihydroxys i lanes undergo 1.2-si L y l m i s r a t i o n t o g i v e a - s i L y l a ldehydes and

ketones.

The one s t e p g e n e r a t i o n o f a - l i t h i o ( M e 3 S i ) a L k a n e phosphonates p r o v i d e s f o r

a convenient r o u t e t o t h e i r d i c r l k y l and v i n y l d e r i v a t i v e s , t h e L a t t e r a l s o

resu l t i r i cJ f r o m t h e P e t e r s e n o l e f i n a t i o n o f c t - s i l y t s u b s t i t u t e d phosphonates,

and g i v i n g d - h y d r o x y e s t e r s w i t h i)su4.53 8 - S i L y L groups s t a b i L i s e carbonium

i o n s formed o n s o t v o l y s i s o f cis- and trans-cr le S i )cycLohexyL e-bromohenzene

su lphonates and Me3SiCH CH OCH2CL p r o t e c t s i m i d a z o l e s as /J-Me3Si ethoxymethyt

d e r i v a t i v e s t o e l e c t r o p h i t i c s u b s t i t u t i o n . Whi le s i L y L a t i o n o f (RCC0)- w i t h

OiitMe S i c 1 g i v e s o n l y t h e s i loxya lkyne, b o t h 'ct3GeCL arid Bun SnCl forrn t h e 2 k e t ene de r i v a t i ve exc t u s i ve 1 y .

P(CHZSi'"e3),., (n=3,1,2) g i v e

2 6 4 3

38

- - 51

5 2

3 2 2

3 54

d - S t a n n y l m e t h y l k e t o n e s r e s u l t f rom R 3 S n C H L i and e s t e r s , f 9 - s t a n n y l 2 hydrazones a r e o x i d i s e d NBS t o d iazocyc topropanes which i s o m e r i s e t o pyrazo-

Group ZV: The Silicon Group 89

l i n e s i n t h e p r e s e n c e o f SnC12, a n d p - s t a n n y l c a r b o n y l compounds g i v e

cyclopropanone d e r i v a t i v e s which r e a d i l y y i e l d d,P- and ~ , ~ - e n ~ n c s . ~ ~ ~ - S i l y l

and p - s t a n n y l c a r b o x y l i c a c i d s d e c a r b o x y l a t e w i t h r e g i o s e l e c t i v i t y t o t h e

o l e f i n , p-R3Sn p r o p i o n a t e s u n d e r g o h a l o g e n exchange a t t i n w i t h Fle3SiX

(X=Cl , I ) , w h i l e CL3SnCH2CH2CO2Pri i s c h e l a t e d w i t h two Sn-Cl and one S r r C

bonds e q u a t o r i a l . MeCN g i v e s a 2:l complex by b r e a k i n g t h e c h e l a t e r i n g .

Med3-nSn(CH2)3SOEt (pl,3;X=Cl,Br) show s i m i l a r c h e l a t i o n f o r ~ 1 . 2 . ~ ~

or-?Phenylthio)si l a n e a n i o n s have been useu t o p r e p a r e alkenes, ketones,

s i l y l c y c l o p r o p a n e s and add 1.4- t o ol,p-unsaturated ketones.57 o t - S i l y l a r y l

ke tones g i v e t h e t h i o k e t o n e w i t h H2S, PhgSi (Ph)C=S (mp 98-10OoC) o x i d i s i n g t o

Ph3Si(Ph)C=S=0 (rnp 13IoC) w i t h MCPUA. The t h i o c a r b o n y l y l i d e RcH-$=CH2 can be

genera ted from I.le SiCHRS (G)CH2SiHr3, and H2?-i=CH2 f rom Me3SiCH SH, (CH20)3

and HCl, u s i n g F- and 1,3-dipolar addition^.'^ 2-Cyclopentenones r e s u l t f rom 3 2

l-(MejSi)-l-(PhS)methylcyclohexene w i t h K C O C l / A l C L 3 , and I-PhSCH2-cycloheptene

from 2-Me3SiCti 2 ~ y c l o h e p t a n - l - o n e . ~ ~ ( M e 0 ) p e S i (CH2l3SH adds t o f l u o r o - o l e f i n s ,

i n d u c i n g p o l y r n e r i s a t i o n i n some, w h i l e 1,3-dithianes a r e r e a d i l y s t a n n y l a t e d

a t p o s i t i o n 2.60 The s e l e n i d e s Me3MCt12SeR r e s u l t f rom rle MCY2X and LiSeR, and

g i v e t rans-complexes L2MC12 (I.l=Pd,Pt) w i t h i n v e r s i o n a t Se i n s o l u t i o n .

The k i n e t i c s o f t h e t h e r m a l rearrangement o f ClCH2SiMe2ii i s explained, and

t h e r e l a t i v e c o n f o r n a t i o n a l e n e r y i e s de termined f o r v a r i o u s mono-, di-, and

tetra(halomethyl)silanes.62 BrCH2SiMe2Cl i s used i n t h e r e g i o and s t e r e o

c o n t r o l l e d s y n t h e s i s o f 2,2-hydroxylated s t e r o i d s i d e chains, w h i l e c leavage

o f Me3Si CH X by e l e c t r o p h i l e s depends on X .63 Ph3S i Car Ore decornposes

q u a n t i t a t i v e l y a t l l f l ° C t o g i v e Ph3Si3r, CO and Rear v i a t h e carbene, b u t

Ph3SiCHBrOMe a t 15OoC g i v e s m a i n l y p r o d u c t s o f 1,2-phenyl and tleO

m i y r a t i ~ n s . ~ ~ Base c leavage o f d i - and t r i h a l o a e t h y l y e r m a n e s i s compared w i t h

t h a t o f S i and Sn, u h i l e R-SnCH I r e a c t s w i t h n i t r i t e by an i o n i c tnechariism,

b u t w i t h cyan ide t o g i v e r a d i c a l s and r a d i c a l anions. R e d u c t i v e l y c o u p l i n g

61 3

2 2

5 2

Me SiCtiBr w i t h Fle S n C l u s i n g lCg g i v e s ?ie,SiCH(SnHe3)2.65

Fle3M?HCr.r w i t h Me3MX (M=S i and /or 6 e ) g i v e s t h e b i s - s u b s t i t u t e d

a c e t o n i t r i l e s which y i e l d d - s i l y l o r d-yertnyl-ol-cyanoalkenes w i t h RCH0.66 For

C(KejSi)2C1~12Y,;' (R=Ge,Sn), t h e s tanny lene has t h e s m a l l e r CMC angle,

3 (We C 1 b:CH(Sirle3)2 shows a s h o r t 11-C d - b o n d (M=Nd), a n d s h o r t M---CH

i n t e r a c t i o n s (l:=lJd,Y), and g i v e s Ctr:e C 1 r41i12 and li2.cj7 Na.rI (CO>1(3

(M=Cr,Mo,W) reduces (fle S i ) CHPCl, t o t h e diphosphene, w h i l e (tie S i ) CHLi and

Me c (Cl)GeW(CO) g i v e t h e s i l y l m e t h y l ger rny lene complex w i t h W-Ge b o n d

len f i then i ng .6iJ

3 2 3

5 5 2

5 5 2 L L 3 2 L 3 2

5 5 5

2 The s i la-Punnerer rearrangement of TsiSPle u s i ny RCPDA g i v e s (MejSi)2C(SKc)


and t h e b i s - s i l y l ke tone (3e3:i)2C0.69 W i t h pmdeta, (THF)4L i+L i (Ts i )2 - g i v e s

t h e a n i o n s t a b i L i s c d b y ymdetaLi (p-CL)Lipmdeta+ w i t h a L i n e a r L i C L L i br idge,

and u h i l e C(tleOMe2Si)3CLi12 shows L i b r i d y i n y t h r o u y h t h e r4eo groups,

(Ts iS iMe20L i .THF)Z h a s a L i 2 0 2 b r i d g e b u t i s a t e t r a m e r i n

(Fle S i ) C(SiMe O H I Z undergoes i n t r d - and interrnoLccuLar H-bonding t o g i v e Long

chains, and TsiOH r e s u l t s f r o n TsiD(Ok1)2 and H202.71 \ $ h i Le T(MeZPhSi)3CZnl)ti11

occurs as a h y d r o x i d e b r i d g e d dimer, (Tsi In)4(0H)6C has an adanantane- l i ke

s t r u c t u r e wi th t h e i s o l a t e d o x i d e i n i t s cen t re . Reducing

In (THF) j -~ -CLIn(Ts i )C12 w i t h LiALH4 g i v e s ( T s i I n ) 2 H 5 L i (T t iF l2 as a h y d r i d e

b r i d g e d 6-membered r ing, a s t r u c t u r e thouOht t o he adopted by a l l t h e group

I11 d e r i ~ a t i v e s . ~ ~ Anchimeric a s s i s t a n c e by 8 - v i n y l , a z i d e and methoxy groups

makes t r i s - s i L y l d e r i v a t i v e s so s u b s t i t u t e d more r e a c t i v e t h a n TsiSiMe21 t o

a t t a c k b y CF3Cti,0H, F,CCO H, and Ag s a l t s , w h i l e 8 - a 2 C C F 3 p r o v i d e s L e s s

ass i stance t h a n 8 -0Me.

D i m e t h y l - a - 1 - p r o p e n y t v i n y l s i l ane cL i l3 ina tes Me S i : o n h e a t i n g t o g i v e

- c i s - and t r a n s - p i p e r y l e n e s a s i Lacyclopropano i n t e r m e d i a t e . V i n y t s i Lanes

can be s y n t h e s i s e d i n one s t e p f rom a lkenes and s i l a n e s u s i n g Ru3(CO)

c a t a l y s t t h r o u g h H2 e l i m i n a t i o n , u h i l e those c o n t a i n i n g a lkene o r epox iae

f u n c t i o n a l r e s u l t on c o u p l i n g 2,3-dichloropropene 2nd aLLyl!;gi>r. V iny tS iMej

s i v e s ~ - 1 4 e 3 S i e t h y l s u l p h o n y l c h l o r i d e s w i t h :.laHSO3/PhCO58ut and PCL5, which i s

used t o p r o t e c t 1' and 2' arnines d s sulphonamides, F- r e g e n e r a t i n g t h e amine,

w i t h i;le S i F , C2H4 and S O 2 The f a c i l e c o n f i g u r a t i o n

i s o i n e r i s a t i o n o f 7-s i l y l - I - a l k e n y l l i t h i u i d e r i v a t i v e s i s thought t o r e s u l t

th rough a s y n e r g i s t i c o r p u l l - p u s h i n t e r a c t i o n of t h e L i -C -bond, and a n empty

o r b i t a l on s i icon.^' d - s i t y l v i n y t c u p r a t e s g i v e syn-ant i -P ,a -unsatura ted

b l y c e r o l d e r i v a t i v e s f rom g l y c e r a l d e h y d e acetonice, and a l l i t o l hexaaceta te

from 3-erythrose, w h i l e atkyr lps g i v e 8 - s i L y l a t e d v i n y l c u p r a t e s which

themselves y i e l d f u n c t i o n a l i s c c ! d ienes w i t h e l e c t r o p h i

3 2 2

73

2

12 as

3

d - F l u o r o k e t o n e s a r e formed from 1.2-dif L u o r o v i n y l s i lanes {)s ing :1.SO L 4' c h t o r o f t u o r o v i n y l s i Lanes f rota F2C=CCL2, and u h i l e v i i i y l s i Lanes add

C I I (C;i2)2Stl 1:1, r i t h (5tO) P ( 3 ) 1 1 an6 AIOr:, v iny lS iMe3 g i v e s :mLynirr.77 The

s t e r e o c h e c i i s t r y o f i o d o d e s i l y l a t i o n of t c r n i i n a t ( E ) - v i n y l s i l a n e s v a r i e s w i t h

t h e amount of L e u i s a c i d c~sed, so 2 i n s e c t iheroii iones o f r iof incc? E/Z i s o m e r i c

r a t i o c o u l d be prepared.75 V i n y l s i l a n e s a r e u s e d i n t h e $ r e p a r a t i o n o f

a l i y t i c a l l y u n s a t u r a t e d oxacyc li cs and 6-azahi cyc LoC3,Z.l S o c t a n ~ s . ~ ' The

I; i n e t i c resc l u t i on o f K 1-1 - (Me3rJ i ) a L k-I-2n-3-01 by t h e S ha r p l e s s process

a f f o r d s an e f f i c i e n t method f o r p r e p a r a t i o n o f 4 p o s s i b l e s te reo isomers o f

secondary a lcoho ls , u h i Le t h e s t r u c t u r e o f (E)-2-butyl-3-Ph3Si-2-propene

h 13 2


n i t r i l e g i v e s S i - C 186.9+0.4p1n.~"

V i n y l s i lanes and stannanes r e s u l t f rom Phi'ie2S iE€ t 3 L i o r Ph3SnBE t 3 L i w i t h

acetylenes, u h i le t r i s u b s t i t u t e d v i n y l s t a n n a n e s o f h i g h s t e r e o s e l e c t i v i t y a r e

formed s i m i l a r l y . " They a l s o f o r m b y condensing a r y l ke tones w i t h

t3un3SnCt~(Si~~leg)R, and w i t h A r r J Z t s a l t s i n t h e presence o f Pd(0) g i v e

(L)-PhCH=CHAr.82 The h i n d e r e d v i ny ls tannanes Me2Sn(RC=CMe 1

fo rm as a m i x t u r e o f ro tamers separab le b y c r y s t a l l i s a t i o n .

A L l y l s i lanes r e s u l t w i t h r e g i o c o n t r o l f rom p - s i l y l e n o l a t e s and a r e used t o

p repare t h i c n s r n y ~ i n , ~ ~ carbapcnam a n t i b i o t i c s , 2 l -hydroxyprogne~terone ,~~ and

a n e x t e n s i v e range of c y c l o a l k a n e s and a-Pheny lse leno

a l l y l s i l a n e s a r e i n t e r m e d i a t e s i n t h e p r e p a r a t i o n o f 8 - a c y l a t e d v i n y l i c

selenides, w h i l e t h e e l e c t r o c h e m i c a l o x i d a t i o n o f a l l y l i c s i Lanes i n t h e

presence o f -W compounds r e s u l t s i n a l L y L c l e a ~ a g e . ' ~ A c e t a l s coup le w i t h

a l l y l s i lanes i n t h e presence o f n o n t m o r i l l o n i t e , w h i l e Rh(1) o r Ir(1) cata lys t?

(R=naphthyl,Ad) $3

t h e i s o m e r i s a t i o n o f s i l y l o l e f i n s t o alLylsiLanes.'i3 (2-Pie..SiCIi a l l y l P i i i 3 r ) . 2 2 2 g i v e s Me SiCtI C(=CHZ)CH2R w i t h RX, w h i l e o p t i c a l l y a c t i v e a t l y l s i l a n e s r e s u l t 3 2 f rom t h e Pd c a t a l y s e d r e a c t i o n o f Or-si LylSenzyL o r l - ( s i l y l ) ? t h y l G r i g n a r d

reayents and s l k e n y l bromides." p-Si L y l a t e o aLkenes a r e a t Least l o 4 t i n e s

inore r e a c t i v e t o i\r,P:eC+ t h a n propene, w h i l e t h e s t r u c t u r e o f a l l y l s i l a n e s has

The p h o t o l y s i s of alLyLMR3 (K=Si,Ge) w i t h p o l y h d l o a l k e n e s induced a d d i t i o n

o f R X t o t h e doub le bonu, w i t h 2 ueCH Ctl=CIlPh i s o i n e r i s i n g t o 7,,GeCHPhCN=CR2 on

i r r a d i a t i o n . ' " 3 0 t h a l l y l s i lanes and stdnnanes a r e used t o nakz pyranonaphtho-

quinr;ne r e s i d u e s o f a n t i b i o t i c s and 2-PlejSiCt12 and 2-Fe SnCH a l l y 1 carboxy-

l a t e s f o r t h e uL id i t io r i of t r i m e t h y l e n e methane t u hc teroa tom u n s i ~ t u r a t i o n . ~ ~

5 2

3 2

A l t y l s t a n n a n e s have been preparec' o u a n t i t s t i v e t y by u l t r a s o u n o u s i n g a

L3drbisr- type reac t ion , and from L i - 6 - s t a n n y l enolatcs, anc R C W r e s u l t w i t h

~ t e r e o s e l e c t i v i t y . ' ~ They a r e a l so for incd as i r i t e r n ? r ; i a t e s i n t h e Pc c d t a l y s e d

c o u p l i n g o f a l l y t i c ha l ides , and i n t h e e l e c t r o p h i l i c d t t o c k o f carvotanace-

t o l s and p i p e r i t o l s . 3 4 They a r e a l s o i n t e r m e d i a t e i n t h e s y n t h e s i s of

a L l y 1 q u i nonzs t r t rahydropy r ro les,

1,5-dierr4-ots anci tetrahyciropyrans.95 2 - S u b s t i t u t e c a l t y t s t a n n d n e s a r e used

i n f r e e r a t l i c d t C-C aonci fo rmat ion , vJhi le c a l c u l a t i o n s dnd P.E.S. suppor ts 96

U-X i n t e r a c t i o n i n E~_gCL_SnCh2C~=Cil*, t h e inore f o r t : r k and i r tc reds i r ig n.

O p t i c a l l y a c t i v e 2' h o m o a l l y l i c a l c o h o l s r e s u l t f r o m RCt tO and a l l y i t i n

compounds, whi Le s s t e n o x i d e e L i I n i n a t i o n f rom 3un3CHHCH CHiipSeAr g i v e

p redom i nent Ly honoa L 1 y L s t dnnaries .

and yu i no Ls, d -met hy Lenr- 8 - l a c t mes,

2 97

S i L y l a lkenes a r e used i n t h e p r e p a r a t i o n of (Z)-hemeicosane, a h o u s e f l y


pheromone, i n c a t a l y s e d c r o s s - c o u p l i ng w i t h a 1 k e n e ~ , ~ ~ b i cycloC3.3.0loctane

d e r i v a t i v e s , c i s - f u s e d r i n g s f r o m c y c l o h e x e n y l s i lanes, 2 -s i ly l -3-butenoates,

w h i l e l-Ke3Si-1,5-hexaGiene-3-ones p h o t o c y c l i s e w i t h b o t h 1,5- and 1,6-closure

u n l i k e t h e l-But d e r i v a t i v e wh ich gave o n l y t h e former.99 UF3.0EtZ c a t a l y s e s

t h e RCHO a d d i t i o n t o cyclohex-2-enylstannanes, and t h e cyc lohept -2 -eny ls i lanes

and stannanes a r e p r o t o n a t e d t h r o u g h s t e r e o s p e c i f i c 8 - a n t i a t tack . lCO

T i ( I V ) c a t a l y s e s t h e s t e r e o s e l e c t i v e p r e p a r a t i o n o f s i l y l s u b s t i t u t e d

1,3-aienes f rom a l l y l s i l a n e s and RCttO, o r f rom d - a l l e n i c a l c o h o l s on

reduct ion, and w h i l e 2,3-disi lylbuta-1,3-dienes a r e formed f rom d - a r

v i n y l s i lanes, a t t e m p t s t o p r e p a r e 2-Me3Si-buta-1,3-diene f rom

ble(MaCO) CH(Ple3Si 1 C=CH2 gave i n s t e a d 3-Me3Si-l ,3,7-octat r i e n e t h r o u g h Pd

c a t a l y s e d d imer isa t ion . ' " Bonded t o t h e Fe(Cr)I3 residue, t h i s d iene can be

t e r m i n a l l y endo acylated, whi l e /?J - b r o m o a l l y l s i lanes coup le w i t h

t i2C=C(A9Ur)C~21~MeZ i n t h e p r e s e n c e o f N i (11) t o y i v e t h e 2 , Z ' - b i s a l l y l

d i r a d i c a l syn thon en r o u t e t o 1,2-dimethylenecyc 10hexanes.~' '~

I - R A-2,4-pentadienes r e s u l t as a n i s o m e r i c m i x t u r e f rom p e n t a d i e r i y l - l i t h i u m

and R3:1Cl (bl=Si,Ge,Sn;R=Me,Ph), and gem-d imeta l l i c d - s i l y l and d - s t a n n y l

d e r i v a t i v e s a r e i n t e r m e d i a t e s i n t h e y r e p a r a t i o n o f s t a n n y l s u b s t i t u t e d

(E 1-enes and 1 ,5-dienes.lU3 2-8un3Sn-Suta-1 ,3-Jiene g i v e s D i e l s - A l d e r adducts,

t h e r e g i o c h e m i s t r y o f c y c l o a d d i t i o n b e i n g de termined by t h e a c i d c a t a l y s t ,

d h i l e a ry loy lnaphthoqu inones g i v e t h e t e t r a c y c l i c 11-deoxydanomycinone w i t h

3

Ile S i C E C P g i v e s d - k e t o e s t e r s o n o x i d a t i o n w i t h Os04, o t - h a l o a c y l s i lanes on

hydroborat ion, o x i d a t i o n anr: h rominat ion , 2 ,2 -d isubs t i tu ted v i n y l s i lanes w i t h

A r I / P d ( I I ) , and anhydr ides and amides from d iac ias , u s i n g t4e3SiCiCOEt as a

dehydra t ing agent.'"6 H y d r o a l u m i n a t i o n g i v e s a l l y l s i l a n e s f rom CCCH kle S i C r C R

w i t h s t e r e o s e l e c t i u i t y , p n o r a c a n t h o l i d e 1, a 13 membered lactone, i s made by

u s i n g a c y c l i c oxy-Cope rearrangement, and a l k a l i n e c leavage o f Si-C i n s i l y l

a lkynes p r o v i d e a p p l i c d t i o n s t o s y n t h e s i s o f epoxyhexenynes, whi l c

t:e SiCXSit1e3 and t.102+RFi g i v e rle S i C r C r 4 O 2 i n yood y i e l d ?

Pd (11) c a t a l y s e s t h e cyc 1 i sc t i o n o f 1 -rk-l- (2-Ple,S i CrCI-2-propenyl a c e t a t e

t o s i l y l c y c l o p e n t d d i e n y l dcetdtes, Cp T i c 1 /IleAlCL, ddds t o Fle3Si CECPh y i v i n g 2 2 Cp2Ti (Sil~e3)C,'C(Fie)Ph+AlCl~- and TiCL4/EtALClZ inddces t h e c y c l o a d d i t i o n o f

t.le S i Cs CS i Me3 t o no r b o r n a d i ene, t h e b i c yc loC4.3.01 nona t r i ene i somer formed

u e p e nd i ny upon t h e t em pe r a t u re used . "' C P C O ( C O ) ~ c a t d l y s e r t h e d i n e r i s a t i o n o f Me3SiCsCSiMc3 t o t h c butauiene, and

t h e C2+2+21 c y c l o a d d i t i o n o f s i l y l a t e d e m d i y n e s t o g i v e t h e A r i n g o f

3

2 2

3 3

3


aromatic steroids, wh i l e CpCo(C2ti4), and ii?3SiCsCSiK,:pJ g ives s i l y l m e t h i n e

complexes. Pd/CuI c a t a l y s e s t h e y n i s a t i o r i o f C6Ur6 u s i n g Me3SiC~Cti, t h e

hexayne d e r i v a t i v e y i e l d i n g the t r i s ( l enzocyc lobu t~d ie r i o ) benzene on C p C ~ ( t r ) ) ~

cata lysed a d d i t i o n of I:egSiCECSiMe which shows more bond l o c a l i s a t i o n i n the

c e n t r a l r i n g than the ou te r ones.’” Photoox idat ion o f 2,3,7,B-(Ne.Si) benzo-

C3.43cyclobutaC1,2-bIbiphenyLene upen the middle benzene r iny, whi l e

2,3,9,9-(Me,Si)4C43phenyl~ne r e s u l t s through coupl iny rle3SiCrCH t o te t raha lo -

phcnylenes, f o l l owed hy cata lysed c y c l i s a t i o n w i t h rle3SiCzCSnilej, and mixed

s i l y l s tannyl acety lenes used i n t h e f i r s t photochemical envelope isomerisa-

t i o n o f a l a t e t r d r i s i t i o n meta l buta-l,+diene complex through t r i p l e stereo-

chemical LdbelLing.”a [ joth WC16 and IloCL5 form s i l y l a l k y n e cori$lexes, whi l e

r i n g s t r a i n i s cont rasted i n €Me S i C ~ C S i ~ ~ e ~ ( C I - I 2 ) d 2 , where c = l - 4 , whi le PIES

and UPS support o r b i t a l s h i e l d i n g by the two Me3Si groups of (Me,Si) C ’I’

Propargy ls i lanes a re used i n the synthes is o f 3-v iny l idene oxolanes, carbeth-

oxy subs t i t u ted unsaturs ted silanes, gabaculine, a s u b s t i t u t e d cyclohexadiene,

dnd leuko t r i r r i e A 4 ano B4 synthesis, wh i l e coupl iny d l l y l o r prop-2-yny ls i l -

anes t o enones and dienones g ives b i cyc loundecenones or bicyclononanones.’12

The molecular dynamics o f H3GeCzCH are assesssed and Me SnCECI1 shows Sn-CZC

t o be s h o r t e r t h a n Sn-CH3 by 1 . 5 ~ m . ” ~ 3ut3SriCsCSnKe, i s cleaved by X 2

(X=Br, I ) e x c l u s i v l y a t Me3Sn-C, whi Le R2NCsCSnR3 reacts r e a d i l y w i t h

e lec t roph i les.’14 A s e r i e s o f stannylethynylboranes have been prepared as

in termediates f o r the synthes is o f S i and N s u b s t i t u t e d h e t e r o c y ~ l e s . ’ ’ ~

1-p-tleC H SO C X S n R 3 adds t o dienes which g ive v i n y l t i n d e r i v a t i v e s on

desulphonylation, whi Le with Pb(OAcI4, alkynylPb(iV) intermediates substi tute

t - d i ca rbonyl n i t ronates.

5 4

2

4 2 2’

3

5 4 2

116 -

F c leavdge o f p-(Me3SiCH 1 benzenes g i v e s 2 - x y l y l e n e i n s o l u t i o n .

I‘le CH f4cJCL adds t o mononitroarenes, cyclohexadiene then o x i d i s i n g t o the

s i l y l r n e t h y l n i t r o a r e n e . l l 7 (Me2Sili)6C6 has C6,, geometry whi Le C6ar6 and

Me3GeCL w i t h Mg form (Me3Ge)6C6 and C(~~e3Ge)2C=C=C(GeMe3)232, the former w i th 113 C symmetry and Me Ge groups a l t e r n a t i v e l y above and below t h e r i n g .

4,3,5-MeCO(ReO)~C6H2SiFle3 i s cleaved a t 4 by AcCL/ALCL3 , a r y l ha l i des an6

ch loros i lanes can b e e l e c t r o l y t i c a l l y coupled, whi l e iodaphenyl a lan ine

r e s u l t s from the m i l d i o d i n a t i o n o f the appropr ia te a r y l s i l a n e . l l Y Boron

ha l i des are r e a d i l y a ry la ted us ing ArSiMe3 and the complexes

Ar(rle3SiC H )P t (PPh3I2 prepared, whi l e the d i r e c t d ias te reose lec t i ve C r

c o m p l e x a t i o n of m-(MeO)C6H4CH(R)OH d e r i v a t i v e s can be ach ieved by r‘ie3Si

i n t roduc t i on .

Funct ional ised a r y l s i lanes r e s u l t from 1,8-diiodonaphthalene by s i l y l a t i n y

2 2

3 2

2 3

6 4

120


i t s t i t b r i o d e r i v a t i v t ? u i t h !la CiOSb CF,, u l i i l e U - s i l y t - I -naphthyL)d i rne thy l -

bordrics furril f t u o r i d e complexes a t boron, s t a b i t i s e d th rough p a r t i c i p a t i o n o f

t iyperva t e n t s i t i con, p a r t i c u t a r t y i f f t u o r i ne s u b s t i tutpcd i t se 1f.l" s i n g Le t

e x c i t e u 9-rl.'3si-ar1ttlracene i s p r o t o d e s i L y l a t e d i n fieail, w h i t e d i - (9 -an thryL) -

c,crtaanc and S e n z y t s i l a n c s underso C4+ i? l in t ramotecu la r s t l d i t i o n s ori i r r a d i a t i o n

which reverses on h e a t i n y . T e t r a - 3 - p h e n a n t h r y t t i n and t h e d i c h l o r i d e l iave been

''3" 2 J

:ilildt. .I '' E - B U ~ ~ S n-sty r y t cop0 tyniers r e s u t t f rom ti)? stanny I s t y r e n e anti sutJst i t u t ed

o l e f i ns, dnc; a r e a c t i v e aga i n s t i:ia r i nc f ou L i rig. (+hi nornet h y l ) riepht h y l s i Lanes

a r e 5 - c o o r d i n a t e a t s i l i c o n w i t h l i e q ~ a t o r i a l . " ~ G r o u p I V s u b s t i t u t e d

1,6-mcth~noC1'3l~r i r1ulenes undergo i j r o t i o & s u b s t i t u t i o n 35 t i n e s (En) and 7X3 t i m e s ( S i ) more r;.adi Ly t h a n s i m i t a r t y s u b s t i t u t e d n;phtiiaLeries."-' A s e r i e s

of s i L y l a t e d 2-CF7-phenothiazines h a w been prepared, 2-ble,Si CH. C H Z O C H Z C L

( S E N ) us?d t o p r o t e c t l i y r r o t e s and i n d o l e s a t n i t r o g e n t o ? - L i t h i a t i o n ,

f o l l o w e d by e t e c t r o p h i l i c s u b s t i t u t i o n , and I-Ce.SiCti,-aroLes t i e s i l y t a t e d by

i t c , g i v e t h e d n i u n Hh ich adds t o c a r b o n y l compounds, rJhiLr ttre d c i d i t i e s o.f

2-Fe u n s a t u r a t e d h e t e r o c y c l e s a r e de termined by desi i . y l a t i o n o f t h e

";>;iro!jri,ite s i Lylc iPthyt i l c r i ~ ~ ~ t i v o . ~ ~ ~ i : - i ie thy t~ .y r ro tes a r e s i t y ta tsd p &nc,

rie. ~ SidSO. CF. ~ a s c a l c u t a t i o n s i n d i c a t e , s i l y t / s t s n n y l t h i a z o t e s used a s

t h i a z o l y t syntnons, 3 -s i l y t d i h y d r o f u r a n s prepared f rom a t - a t t e n i c a l c o h o l s and

o x i d i s e d t o f u r a n s and furanones, whi Le p o t y c y c l i c a romat ic d e r i v a t i v e s r e s u l t

f rom arynes and h i s - s i LyL n;tghthafurans.12"

2,6-3is( t i t h i o t r i r n e t h y l s i L y 1 n e t h y L ) p y r i d i ne.ZTME D A i s r e a d i l y o b t a i n e d f rom

?,6-(FIe S i C H C H,tf and e x h i b i t s doub le ( ~ 3 - a z a a t L y L ) - l i t h i u r n bonding.

S t r u c t u r e s o f MCIK t i C(SiMe 1 -212 (I?=:.lg,Zn,Cd,Hg) show WIJ bond ing o n l y f o r

Ivl=ll~, and C~i2(CL)ZrCii(Si!1e ) 2 (R=2-pyridyl,ChHqPPh2-0) reduce t o t h e Z r ( I I 1 )

d' spec ies and complex w i t h Me3P.Iz7 2-Me !PIC H CHSiMe3 a n i o n complexes w i t h

Pd, w h i l e (P1i3P)4Pd c a t a l y s e s t h e c o u p l i n g o f s t a n n y t p y r i d i n e s w i t h

b romopyr id ines t o G ive b i - and t r i ; > y r i d i n e s .

1 + i t h o x y c a r L 1 o n y l - 2 - s i l y l a z i r i d i n e s r e s u l t on add ing t h e a p p r o p r i a t e n i t r e n e

t o v i n y t s i l a n e s , d , p - e p o x y s i l a n e s r i n g open w i t h Me S i N 3 t o g i v e t h e 3 I -aminoalker ie synthon, i n t h e gas phase r e g i o - and s t e r e o s o l e c t i v o t y , w h i l e

d-t.le3S i-#,/3 - e p o x y a t d e h y d e s g i v e 2'. a Lcoho I s w i t h G r i g n a r d r e a g e n t s . 29

S i l y l c y c t o p r n p e n e s a r e formed from s i lyL(bromo)cyclopropanes, and coup le o n

o x i r i a t i o n o f t h e i r CuLi d e r i v a t i v e t o Give t h e s i l y t s u b s t i t u t e d octa-2,h-

d i ene-4-yne o n h e a t i n9.I3O The I - s i Lyl-2-netkiyt t hio-3,3-dirnethy l c y c Lopropene

g i v e s t h e I-si t y l i n e t h y t t h i o a t l e n e on i r r a d i a t i o n w h i t e perbenzo ic a c i d

o x i d i s e s I -Me3Si-cyctopropene t o CL -Me 'Ji- &,p -unsatura ted ketones.

'> I

2 2

5 - -

3 2 2 5 J

5 4 3 2 3

2 6 4

122


S u r p r i s i n g l y , n i t r a t i o n o f l , l - (Pr '3Si )2benzocyclopropene s u b s t i t u t e s t h e

benzene r i n g w i t h no a t t a c k a t t h e cyc lopropene r i n g .

5 - S i t y l s roups s t a b i l i s e carbonium i o w throurJh encourag ing rit16 c lusurc ,

whi l e t h e 1 - (Me3S i ) c yc topropy 1 r a d i cd L i s p lanar . 32 1,2- (I?egS i 2cyc l o p royane

a f f o r d s t rans-monosulahonyl and -acetyL d e r i v a t i v e s w i t h o u t r i n g opening, b u t

d i a c y t a t i o n g i v e s b i f u n c t i o n a l butanes. Me3Sicyctopropane r i n g opens t o g i v e

m i n t y t h e a t t y l s i l a n e , w h i l e Pd c a t a l y s e l t h e c o u p l i n g o f a r y l and v i n y l 1-1.-

hal ides, a r c R C O C L w i t h Zn homoenolates Cfrom 1-RU(1-r~le3SiO)cycLopro:~ane3. >'

FVP o f 5-3r-6- ( I k , S i 1 h i cyc loC3.1 .O1 hex an? g i v e s suppor t i ng evidence f o r t h e

i n t e r m e d i a c y o f cyclohexa-1,2-diene, whi Le s i L y L a t i o n o f c a r b o x y l i c a c i d

d i a n i o n s l eads t o l i n e a r anc c y c l i c a - s i t y l acids.'54 S i l y t m c t h y l c y c l o p r o p a n e s

r i n g open t o ' j ' iv? cyc lobutanone d e r i v a t i v e s o r 8,s-unsaturated acids, and

U-He S i a c y l c h L o r i d e s w i l l add o l e f i n s i n t h e presence o f TiCL4 t o y i c l d

2-cyc Lopropytcyc l o a I kanones 35 Photo L y s i ng ma l e i c a n h y d r i d e w i t h Me3S i

acety lenes Gives s i t y l s u b s t i t u t e d cyc Lobut-3-ene-1,2-dicarboxylic ac ic i

d e r i v a t i v e s i rh i t e germy lcyc lobutane occurs p r i m a r i Ly as t h e c c j u e t o r i a l

conformer.13" 3 - S t a n n y t - I - s i loxycyc loh?x- l -?nes p r o v i d e t h e syn thon f o r t h e

d i a n i o n o f cyclohexanone, and I-AdGeVe H adds t o H2C=CtlC02Si He3, h y d r o l y s i s

g i v i n g t h e 2-Si l y l e t h y l g t y c o s i d e s underso a I - s t e p s t t : r e o s e t e c t i v e

c o n v e r t i o n t o sur;ar 1.2-t rans-d i acetates, 2-f tuoro-2-pyr imi c j i n y l a r a b i no-

pyranos ides r e s u l t f rom t h e condensat ion o f t h e p r o t e c t e d y l y c o s i d e w i t h

s i l y l a t e d p y r i m i o i n c s , and s i la$- ionones have been

I -Me- I -s i lacyc lobutane r e s u l t s b y condensing B - C l ( C t i ) S i F k ( i l ) C L w i t h F h / K

vapaur, u h i Le 1-fk-1-k - p y r i d y L - I - s i l a c y c t o b u t a n e h y d r o l y s e s f a s t e r t h a n

l - r , le- l -aryL- l -s i l a c y c l o b u t ~ n e s . ~ ~ ~ 1,3-il isi Lacyclobutanes become t h e r m a l l y

more s t a b l e as S i i s methylated, w h i l e t h e t e t r a m e t h y l d e r i v a t i v e r i n g expands

t o t h e 1,3,5-trisi lacyctohexane i n t h e presence o f Z r C L 4 . The s i n g l c t ground

s t a t e o f s i Lacyc lobutad iene i s o n l y Skcal/moLe lower t h a n i t s t r i p l e t s t a t e

(23 k ca 1 /mo L e for c y c 1 obu t ad5 ene 1 .' '!'

131

3

2

2 3

The t h e r n a l y s i s o f s i l y t s u b s t i t u t e d s i Lacyctobutenes i s explored, w h i l e

p h e n y l s u b s t i t u t e d 1,4-disitacyctohexa-2,5-dienes p h o t o t y s e t o b e n z o s i t a c y c l o -

pentadienes.14' A i (3) c a t a l y s e s t h e c y c l o a d d i t i o n o f ( i~e3Si)2(f~es)SiCECPh t o

PhCzCSif.le3 v i a t h e I-si lapropadiene, whi Le i r r a d i a t i o n i n t h e presence o f

i J i ( 0 ) g i v e s t h e s i tacyclopropene, which w i t h PhCzCSiMe3 u i v e s s i l a c y c l o b u t e n e

and s i l a c y ~ l o p e n t a d i e n e . ' ~ ~ A s e r i e s o f n e t a l l a s i lacyc tohutanes (Th,Ti,Ir,Pt)

and a s i l y l a t e d d i t u n g s t a c y c l o b u t e n e r e s u l t s f rom C(Me2CH0)2U(~-C-SiMe 11 and 3 2 c0.143

5 -fit?3SiC5H4Nhti3 and Au(1) g i v e a t r i a n 9 u l a r i4bRu2+ complex, (Me3SiC H ) Zn

5 4 2


shows q5- n1 exchange, rJhi Le C(flejSi)2C5H33jTh i s monomeric. 144

(Ple0)3Si(CH2)3C51i5 (Lli) g i v e s an fLS-LRh(COD) complex e f f P c t i v e as a c y c l o t r i -

m e r i s a t i o n c a t a l y s t , t h e t i t a n o c e n e d i c h l o r i d c complex o n s i l i c a , a f t e r

reduc t ion , i s e f f i c i e n t and s e l e c t i v e f o r h y d r o g e n a t i o n o f alk-I-enes, whi Le

l i t h i a t i o n o f CpFeC I I CHllcllJMe2 w i t h OuLi/TIIED leads t o s i l y l a t i o n o f b o t h

r ings . lC5 :qe2Si(C R 1

Ti,Zr,Ko,W, and F:J4' c h e l a t e s u i t h Lanthanides Sm, fk!, and Lu, nut b r i d g e s

t h e Y b2C L 2 r e s i d u e g i v i ng Crle2S i ( C5R4) 212 YbZC l2

IleduciriG ttlle C S i C l z w i t h L i n a p h t h a l e n i c e Gives decdrnuthyls i l i c o c e n e

which occurs i n t h e c r y s t a l as d 1:2 m i x t u r e o f isoraers w i t h r i n g s p a r a l l e l o r

h a v i n g an i n t e r p l a n a r ang le o f 25.3°.148 C1,2,4-(Me3Si> C H 1 tie: shows t b t

r i n y s a lmost p a r a l l e l , Me5C5GeCL and (rrle,Si)ZXLi (X=N,Ctl) g i v e s t h e mixed

yermylenes Me5C5GeX(SiKe 3)2, t h e l a t t e r g i v i n g s a l t s w i t h a c i d e.g.

lle5C5Ge+BF - and undergo o x i d a t i v e a d d i t i o n w i t h halogens and ileI, MeCdCl,

CF3S331'ir.147' The gerinylene complex Me C (CL)tieW(CO)5 r e a d i l y rear ranged t o

I~egC5Ge+C13GeW(CO)5- whi l e CFieqC5SilieZCgMe4iil and dioxanGeCL g i v e t h e

s2!! (R=t+,i'ie) forms a n e x t e n s i v e s e r i e s o f cor:iplexes w i t h

47

5 5 2

3 5 2 2

5 5 - remarkable i12,T5-complex ( ~ 2 - ~ l ~ 4 C 5 ~ i t l e 2 S i ~ 5 - ~ e 4 C 5 ) ' e + G e C l ~ . I 56

Reducing (F;esC5)2FiCl- 2 (il=Ge,Sn) g i v e s t h e r iccamethyl metal locene, t h e t i t i

d e r i v a t i v e y i v i n g s t a n n y l e n e w i t h (Ple3Si) CHLi and po lys tannanes w i t h MeLi.

The i n t e r m e d i a t e adduct (f11-We5C5)2Snl'leLi can be t r a p p e d w i t h MeX.''' 11.0.

c a l c u l a t i o n s i n d i c a t e t h e lone p a i r i n (Ph5C5)2Sn: t o be 5s' i n ChardCter and

n o t d e l o c a l i s e d i n t h e r i n g s . [(PhCH C 1 #: (M=Ge,Sn,Pb) a l l show "open

mouth" s t r u c t u r e s w i t h ang les o f 31-36' between t h e r i n g s and t h e Lone p a i r

p r o t e c t e d by 3 b e n t y l croups. (C5H5)2M (ti=Hu,Os) r e s u l t f rom C5H5SnBun

t r i q u i n a c e n e and g i v e s i s o m e r i c (Me. S i t ricycloC5.2.1 .04'1Uldecatet raenes on

s i l y l a t i o n w i t h t h e 1,4- and 1,lO- i somers p r e s e n t i n t h e r a t i o 3:2. The

l a t t e r i s t he l e s s s tab le , r a p i d l y i s o m e r i s i n y i n t h e presence o f Me3SiCt .

Reac t ion o f S i F z w i t h cyc lopentad iene ana c y c l o h e p t a t r i e n e i n t h e gas phase

and by cocondensat ion g i v e s a v a r i e t y o f products, those w i t h t h e t a t t e r

p r o v i d i n y ev idence t o d i f f e r e n t i a t e t h e s i l i r a n e mechanism f r o g t h e d i r a c i i c d l

one i n t h e a d d i t i o n r e a ~ t i 0 n s . l ~ ~

C a l c u l a t i o n s i n d i c a t e t h e s i l a c y c l o p e n t a d i e n y l a n i o n t o be more s t a b l e t h a n

i t s Q5-M complexes, w h i l e n.m.r. s t u d i e s i n d i c a t e l i t t l e S i - C t r - b ~ n d i n g . ' ~ ~

2

2 5 5 2

3' The d i a n i o n o f d ihydroacepenta lene u i i d e has been genera ted d i r e c t l y f rom

3 2

P y r o l y s i s o f S i 2 F 6 w i t h buta-1,3-diene g i v e s t h e s i lacyc lopentene, F S'i(CH 1'

and i s more s t a b l e i n t h e t w i s t ( C 2 ) form, w h i l e t h e s t r u c t u r e o f Cl2Si(CH2I4

has been r e i n v e s t i g a t e d i n t h e gas phase (Cs).155 The s i l a c y c t o p e n t e n e r e s u l t s

d4

on condensing diene/Ne$iC12 u s i n g IJz, and g i v e s t h e s i l a c y c l o p e n t a d i e n e w i t h


3r /dehydrobronin&tion, whi If Ph s u b s t i t u t e d s i l o l e s complex

metals. S i l a f Luorerie r e s u l t s f rorn 2,Z'-dihalobiphenyls

condensat ion. lSC

2 w i t h t rans i t i on

on reduc t i ve

p -Func t iona l i sed I - s i la(gt-rna)cyclopent-2-enes have been used as syn the t i c

intermediates, no tab ly the a l l y 1 d e r i v a t i v e s which pyro lyse t o the f i r s t S i - t i

s i 1 0 l e . l ' ~ The 4-metal lospiroC3.3lheptanes r e s u l t from d iGr i yna rd and RC14

(N=Si,Ge), dnd the 5-~ermaspiroC4.43nona-2,7-diene from the dihalogermacyclo-

pentene on condewat ion us ing a l k a l i m c t d S Y S i labicycloC3.2.l loctanes

r e s u l t on coupl ing 1,3-(UrCH2)2cyclopentane w i t h r,le2Sit3r2 us ing r4y, whi l e

halogenation o f 7-s i lanorbornadienes g ives Ke2SiXZ and benzene d e r i v a t i v e s

exccpt f o r BrZ/CC14 a t O°C, uhen 2-bromosi ly lnaphthalene A se r ies

o f si lacyclohcxancs have been made by condensing MeSiX3 w i t h Sr(Cii 1 Or, and 160

C3.1.1lpropellanes br idged by S i , Ge, Sn shoun t o have long b r idge bonds.

S i l y l s u b s t i t u t e d s i lacyclohexadienes undergo s i l y l m i y r a t i o n on coo rd ina t i on

t o Fe(C0I3, and meta l mediated c y c l o a d d i t i o n bf FzS-CUut t o cyclohexa-

1,3-ciiene g ives 3 isomeric adducts.'" S tanny le thyny l s i lanes and yermanes

c y c l i s e on organoborat ion t o g i ve the s i La o r germacycloper&adiene, whi lr

distannacyclohexadienes r e s u l t from ClF:e,Sn(fie)C=C(E t )aE t and LiiEtZ. '"

A se r ies o f a ihenzos i l acyc les r e s u l t by conaensing (@?C H 1 X Cbi=Li,lvlyCl;

X=<CH ) (n=0,1,2), t:lle) iJi t h ch lo ros i lanes, whi le 10-si la-9-oxa-9,lC-dihydro-

phenanthrene coord inates e i t h e r benzene r i n g w i t h the Cr(C9l3 residue, the 2 isomeric complexes a l s o weakly i n t e r a c t i n g w i t h e i t h e r S i o r O.Ib3 While the

d ihenzodise lenasi Lonine shows a t ransannular Si---Se in te rac t i on , t he re i s

none f o r t he germanium analogue. 5,5-0iphenyloctaf luorogermanthrer~e Ph ticC

shows a sho r t 5,b- f l u o r i n c i n t e r a c t i o n o f 241 .7pm.164

2

6 4 2

2 n

2 12%

The pho toe lec t ron t r a n s f e r from f l a v i n analogues t o RqSn (R=alkyl) i s shown

t o have a h ighe r (170kJ) b a r r i e r than t o organic compounds (40kJ), w h i l e

Bun4Sn i s used t o a l k y l a t e WC16.165 ArSnBun3 gives ArCH IJf'rc2 w i t h ile 2 2 k C H

(Mannich react ion) and a r y l a t e s unsaturated a l coho ls t o g i ve cycCic e the rs

CCuCIZ /Pd( I I ) I , w h i l e IN3 c l e a v e s A r 4 S n b u t adds t o h r 3 S n a l l y l . 1 6 6 The

stereochemistry o f i n t ramo lecu la r e l e c t r o p h i L i c a t tack o f RCHO on the C-Sn

bond i s examined, t ransmethy lat ion o f Hg(11) by MeSn and MePb s tud ied as i s

the polarographic behaviour o f t r i and d i s u b s t i t u t e d oryanolead s a l t s

conta in ing Me S i CH2 The mass spect ra o f many tetraorganostannanes

are measured.'68 NMR s tud ies i nc lude methyl t u n n e l l i n g i n the 8-phase o f TMS,

long range coup l i ng i n S i and S n s u b s t i t u t e d organoboranes, 7 3 ~ e and 13c f o r

organogerrnanes, carbon isotope e f f e c t on ' I 9Sn nuc lear shielding, t he

dependance of 117sn-13c coupl ing on CSnC angle, and 207Pb i n soCid Ar4Pb.169

2

98 OrganometaIIic Chemistry

3 C a t e n a t i o n - I Adding 5Pnzyne t o t h e d i s i l o l e PhC=CPhPhC=CPhSi ([?el (Mt.)S iPhC=CPhPhC=ll-'h

g i v e s t h e syn thon f o r d i m e t h y l d i s i l y n e , s i n c e h e a t i n g t h i s b r i d g e d d insphtha-

lene adduct a t Y50°C w i t h anthracene t r a n s f e r s t h e I r i e S i S i i l e residue.17' 29Si

ninr of l l r Z S i = S i A r ' 2 shows a n o v e l i n t r a m o t e c u l d r r e a r r a n g e m e n t t o g i v s

RrAr 'S i=S iArAr ' isomers, Mhi l e Hs(OCOCF312 o x i d i s e s Mes(X)Si=Si (R)Mes t o t h e

1 , P d i a c e t a t e t h r o u g h a d i s i Lene-Hy(I1) adiruct.17' O x i d a t i o n o f

trans-Phi:ieSi=SiMePh i n t h e presence 0.f Ph C a t h i g h tempera ture g i v e s a b3:37 m i x t u r e of i s o m e r i c C2+2l-cycloadJucts. The c i s - d i s i l e n c g i v e s a 3i3:62 m i x t u r e

s u p p o r t i n g a d i r a d i c a l i n t e r m e d i a t e k i t h s low r c t a t i o n o r i n v e r s i o n corqarcu

t o t h e r i n g c l o s u r e process. The f l u o r e s c e n c e o f t h e d i s i l c m (r'le3SiC!! ) S i 2 4 2 shows a l a r g e S t o k e s

The s t r u c t u r e s of KOle S i ) CHI M, (I.l=tie,Sn) a r e suppor ted b y c a l c u l a t i o n s

o n r12H4, s h o r i n g t h a t t h e t r a n s - f o l d e d s t r u c t u r e i s t i l e most statr le.17'

C a t c u t a t i o n s show t h a t s i l y l s i l y l e n e i s i n te r r i ted ie te i n t h e p y r o l y s i s o f

d i s i l a n e t o d i s i l e n e , t e t r a h e d r a l S i 4 H 4 t o be t h e m i n i n u n energy isomer, and

tile resonance s t a b i l i s a t i o n energy of S i L H 5 t c be o n l y 30X l e s s t h a n t h a t o f

C E i i b . tiowever t h e Ur isoar ie isomer i s t h e iiiost s t a b l e .

Evidence f o r t h e r o l e o f d -orb i t ,3 ls i n UV t r a n s i t i o n s i n p h e n y l d i s i l a n c s i s

c o d li c t i !IS .I7' CF..SO,11 nonodewat hy l a t es 1 !e ,S i ,, t h e su Lljhonat e i v i ncj a Lkcjxy

d e r i u a t i v c s redlrri 17 w i t h Li3R/ii lWA o r aLLyl~)tl/Et3i!, w h i l e ZnFZ f l u i l r i n a t e s 'I 76

p t i r n y t c h l o r o ~ i s i l a n e s ( a l s o (FPh-S i ) ,rig G i v e s FPh2SiSiPh2F on i r r a d i d t i o n ) .

The s t r u c t u r e o f 2,4,6-Jut3C,li,SiF. S i : i r l t s Z shows a S i - S i bond Length o f

237.[jpi,l, w h i l e Uut,,Sii ( 1 2 2 lS?°C) ( f roa :3ut3Si- arid %I+ fi Uut3Si') has t h e

L o n g e s t S i - S i b o n d r e p o r t e d t o d a t e (ZG'i.?prii) w i t h s t r e t c h i n g f r e q u e n c y

271cm-' ((Lf. iie,Si

2 2

3 2 41.

174

3 2 c ) L

L L

" - L

177 4%cin-'), and ts t i i , i a t r :d !-iond o r d e r o f 2 . 2 5 . d x i d a t i v e cleavacje o f tl.?lilSi4 proceeds s e q u e n t i a l l y th rough t?rrlnindl b e f o r e

in i t id le S i -S i bonds, t h e idechanism o f p e r o x i d a t i o r i o f d i s i l a n e s exarriined, whi L ?

the i n c r e a s e i n S i - ' i i bonu d i s s o c i a t i o n o n n i e t h y l i i t i o r i of p o l y s i lenes i s

a t t r i b u t e d t o 2nhanced i o r i i c bor id i ng forces, \ J i t t i d-orb i t a t cont r i h u t i u m

as i s t h e t r a n s m i s s i o n o f s u b s t i t u e n t e f f e c t s throui,t i S i

chains.17' The f i r s t C 2 . 2 3 - p a r a c y c l o ~ h ~ n r S r i i c j c J b y 2 p a i r s o f S i dtolns stior

a s t r o r i y C< i r i i x ing b e t w w r i S i - S i bontis and t h e r ings, anti a LarLje rod s l i i f t

i r i t h e JV spectrum. The te t r r l l i i e r i s a t s o For iwi i i n t h e s y n t i i r s i r , u h i l e r i n y

openi ng I ,I , 2 , 2 - ~ ~ - 1 ,?-di s i t a i x n z o c y c t o t u t c r i e g i v e s a po1yi:ier.l"

U L

1,i-13ut:-~,2-CY2Si.,CL / L i yives t he l o n g - l i v e d r a d i c a l anion, arid l i k e

[cy c ~ s i ] . b r ic ;yes ant i l racune 7,s t o g i v e t i l e c i i s i laC2.2.23~cta-2,5-diene. - L 2

2 2


These p h o t o l y s e t o r e l e a s e t h e c y c l o t e t r a s i l a n e . I n t h e presence o f PhCrCH/Li,

t h e d i h a l o s i Lanes g i v e t h e e t h y n y l d i s i lanes and t e t r a s i Lacyclohex-l-ene.18'

(But2Si)g, w i t h S i - S i bone l e n g t h 251.lpm (bond o r d e r 3.541, r e a c t s w i t h I2

t o g i v e t h e L i n e a r 1 , 3 - d i i o d o t r i s i l a n e ( r e c r y s t a l l i s e d from Pr'OH!) w i t h S i -S i

bond l e n g t h s 253.1 and 264.4pm (bond o r d e r 0.41 and 0.321, and p h o t o t y s e i n

t h e presence o f RCH (R=Me,Ph) t o g i v e 3,6-disi la-3,b-di hydropyr im id ines , whi Le

f o r R-Ou t,

l a t t e r has a n almost p l a n a r s t r u c t u r e r i t h s h o r t Si-iJ and l o n g S i - C bonds

w i t h i n t h e r i n g and t h e Larges t endothermic bond ang les a t W and CSiC r e p o r t e d

t o ddte.182 The c y c l o t r i s i l a n e C(Et3Si)2Si33 i s s t a b l e t o O2 and i.1*0, and on

i r r a d i a t i o n g i v e s t h e t c t r a s i L y l d i s i Lene.lZ3

The b i c y c l o t e t r a s i Lane 1,3-RutZ-2,Z,4,4-(2,6-€ t,C c 5 3 4 ii 1 , t e t r a s i t a b i c y c l o -

Cl.l.03butane has t h e h i n g e S i - S i bond (237.3pm) s l i g h t l y Luriger t h a n t h e

o t h e r 4 (232+1pm) and r e a d i Ly undergoes c o n f o r m a t i o n a l invers ion , w i t h r i n g

s t r a i n energy comparable t o t h e carLon The r a d i c a l a n i o n

(PriZSi)4' shows 2 e q u a l l y in tensed-13C o s r s i g n a l s showing t h e r a d i c a l t o be

bent w i t h slow i n v e r s i o n . P e r s i l y l c y c l o t e t r a s i Lanes prepared f rom Ph 2 2 S i c 1 v i a

Ph2Si(SiXe3)2 and (14e3Si)zSiOr2 show tnore i q t e n s e chromophores t h a n a l k y l

c y c l o t e t r a s i l a n e s , whi l e condcnsincJ PhRSiC12 (i?=Rut,LiutCH2) w i t h L i g i v e s a

cyc L o t e t r a s i Lane m i x t u r e c o n t a i n i n g 2 1 t 4 yecimet r i c i soii,ers.135 I r r a d i a t i n g

c y c l o t r i- dnd t r t r a s i lanes i n EtOH i n t h e presence o f F,lO-dicyanoanthracene

g i v e s d f t 0 - o - l l t r i and t c t r a s i l a m s . R e i i c t i v i t y decreases w i t h r i n g s ize,

w h i l e t l t c r i n g s t r a i n energy i n ( K ' R " S i ) (fi=6,5,4,3) i s c a l c u l a t e d as 0,6,23

and 4lkcaC respec t ive ly . "o

2,2,4,5, 5,6-3ut 6-2, 5-di s i La-2,s-di hyc ropy r i m i d i ne r e s u 1 t s . The

-

(lk.,S.i) ( ~ 5 - 1 2 ) under(ji)es acir ; catalysecr i s o m e r i s a t i o n t o lJle S i L n 3

s u b s t i t u t e d G c l o p t n t a - and hexas i lanes, k i t h c o n f o r m a t i o n a l chdnycs. W i i i l e

t.:e,SiCL2/Li i n T H F a t - S O C t o i 3 ' ~ g i v e s (rieZSi),, (E=5-7>, a t 1 1 - 2 5 ' ~ t f i e

s i l o x a n e s (fie2SiO) ( ~ = 3 - 6 ) r e s u l t . Other c h l o r o s i l a n e s u i t h L i i n TtiF a t

35-45OC a l s o eivesn s i l o ~ a n e s . " ' ~ (PhiWii)!, i s r e a d i l y c leaved by H X t o g i v e

- -

(XI,?cSi)h (X=CL,Sr,ORe,F), w h i l e Ele S i X Gives r n e t a l l o d e r i v a t i v e s which 11 6 condense t o y i e l d (r:e,1Si5)2 and (t:ellSi5)ZrJi14e- "" Conformat iona l d r i d l y s i s

c a l c u l a t i o n s shok ( C A Z l 2 t o be most s t a b l e as !Loa t -cha i r b u t (I'le2Si)8 as

t w i s t - c h a i r - c h a i r conformt2r. i i k e u i s e (t;e,Si) (2=13,16) d i f f e r i n

c o n f o r m a t i o n f r o m o t h ? r i s s n d 1 5 m?intrered r i n c ; s . S o t t i e x h i b i t abnor ia i iL

t o r s i o n a l ancJLes, dnc; u n u s u a l l y l a r g e S i S i S i angles, a v e r a s i n 2 115' i n t h e 1 s9 former, i n o r d e r t o r e l i e v i . u n f a v o r a b l e t r d n s a r l n u l a r I.le---fle i n t e r a c t i o n s .

Sond energ ies i n ( X Y S i ) and f.iMK of (hex".Si) a r e .;etcrlnined.lYi'

2 *

I- 11

- L Q A L C L 3 c a t a l y s e s t h e c o r i r e n s a t i o n of PiejSiCL t o HeSi (SiFle 2 C L I 3 , Whi LP

100 Organometallic Chembtry

L i c ~ C S i ( S i M e ~ ) ~ l ~ adds cis- t o acetylenes, h y d r o l y s i s g i v i n g

t rans-HHC=CHS i (S if9e3)j.191 (Me3S i 1;s i L i .3TtiF and M C l3 (M=Ga, I n ) g i v e t h e

c h l o r i d e b r i d g e d compound C(Me3Si). 1 MC12Li (THFI2 , and w i t h o r y a n o s i l i c o n

ha t i d e s t o g i v e (Mc3S i I3S i s i XnR3-fi. "' He3S i m i g r a t i o n i n (tle3S i 1 3S i-CH2Ulle

and (i4e,Si)jGc-CK20Me i s induced b y i3CL3, whi Le p h o t u l y s i n y (Me3Si)3GeC(0)AC

does no: y i f l d t h e i s o r w r i c yerinene b u t d complex i n t r a c t a b l e mixture.'93

(I'le,S i 1 JS i Fe (C0)LCp r e s u 1 t s f roin ( k 3 S i I3S i L i and t h e broiniue, CpFe (CO) zS i We2-

-SiFlc?ft2 y i v e s CpFe(CO)$iRg w i t h itg scrambled t h r o u o h Si=Fe in te rmed ia tes .

The gas :)base r z a c t i o n o f t r d n s i t i o n m t a l i o n s u i t h Me6Si2 induces cleavage

o f t h e S i - S i bond, w i t h m e t a l - s i l y l e n e i n t e r m e d i a t e s

r1*qti,2 utidprcjors C2+21 c y c l o a d d i t i o t i t o a 5 - t t i i a c y c l o h r p t y n e t o g i v e t h e 195

f i r s t d iger inacyclobutcne, whi Le Ge12 g i v e s t h e t e t r c r i o d o analogue. 196 (CLPli G C ) ~ ancl u ~ ~ ~ G ~ ( o H ) condens? t o g i v e t t ie 5-mei,ibered t r i yer indd ioxar ie .

The s y n t h e s i s o f Ph4Ge and Ph6(ie2 b y G r i g n a r d r e a c t i o n y i v e s Ge Ph 3 8 dn(r

ri-be4PI~,3.2C6i+g a s by-products i f excess l i y i s used, u h i l e n-Ge5Ph12 r e s u l t s

from LiGe2Ph5 arid Ph,GeCL2.1(i7 C o n d i t i o n s a r e op t i rn ised f o r inakirig tiejRZPh6

-

2 2

(K=l?e,Ph) f rom Ph lieM (M-Li,K) and K GeCl and Cl(l iePh 1 C L ( ~ = 3 , 4 ) frora

Ph2GeHCL i n t h e presence o f E t 3 , f (A Ph2Ge:).

T i reodi Ly reduces (Uur'3Sn)Z0 t o (Uun3Sn)Z a t 25'C i r i TriF, whi Le (CLPh,Sn),

3 2'193 2 5

' 199 th rough s e v e r a l steps.

t h e s o l i d s ta te , drid k t i i L e

h-meiliberrd ring.""

aria Tie Le(GeH3)4-E ( p l - 3 )

d i ue t 1.ly7 and t r i i : iet ~ i y ~ t r i - LJ I cjcrmanes. Ph.,beSiple Fe(C3I2Cp has a l o n g e r Ge-Si uorid (24C.Spn) ttiari t h a t

i n Ph iieSibie.,., arid t h e s h o r t e r Si-Fe bond (232.;lpm) compared * i t t i t h a t i n

k'ii SiSiP'e FeCCi)) cp s u p p u r t s an enhanced S i -Fe i n t e r a c t i o n . 2 0 2 S i Lylstdnr ianes

l!5Si5:i3un.. (H=fle,Et) c a t a l y t i c a l l y adti c&- t o acetylenes, t h e a lkenes so

formed g i v i n g P - s i L y l J i v i n y l ketones w i t h l?COCL, w h i l e Pd(O) c a t a l y s e s t h e

i n s e r t i o n of I ~ N C i n t o t h e S i - S i i bonrl g i v i n g ii~;=C(Si~te3)SnFie 203 t?e6Sn2 atitis

t o d c e t y l e n e s s i in i Lar ly, t h e (Z)-aLfducts i s o m e r i s i n y t o t h e ( E l - d e r i v a t i v e s

t,~c,SnC(fle)=C(Snfle )COP (R=OEt,lC[le 1 oil heating, w h i l e e n o l t r i f l a t e s g i v e

v i ny t s t a nnd ries .

2

3

3 ' - 2 2

3'

202 2

4 : iycroyen D e r i v a t i v e s

F.T. i o n c y c l o t r o n resonance mass s p e c t r o m p t r y of s i t i c o n c l u s t e r s 3rd IZeSiil..

suppor ts a d e c r e a s i n g r e a c t i v i t y u i t h i n c r e a s i n g c l u s t e r s ize , t h e A l C 1 3


c a t a l y s e d r e d i s t r i b u t i o n o f m c t h y l s i lanes FlenFiH4-n (r32,5) g i v e s a Si- l ie

d i s s o c i a t i o n energy o f 37527kJ, whi l e a & y l s i lanes and h y d r i d r g i v e

hypcrvd le t t t adduc ts i n t h e vapour phase which t r d n s f e r h y d r i d e t o S i i4.205

R e t d x a t i o n t i m e s f o r Si- t i v i b r a t i o n s a r e compare0 f o r v a r i r j u s s i l a n e s

RT: ' i < "S i I i , and t h e S t r u c t u r e and v i b r a t i o n a l s p e c t r a o f C F 3 S i H j and i t s

d e u t e r i o d e r i v a t i v e s a r e analysed, w t i i l e a s e r i e s o f s i l y lmethanes

(R3Si)nCH4-n (5=2,3) ( C l C t l )Ye S i t 1 rear ranges t o We3SiCl by a

concer ted d y o t r o p i c pathway and e t h y n y l s i lane t o v a r i o u s p r o d u c t s t h r o u g h a

s i t i rane i n t e rmedi a t e .207

- 2 2

The t r i p h e n y l s i l y l c a t i o n has now been c h d r a c t e r i s e d as dn i o n p a i r i n Low

p o l a r i t y s o l v e n t s by exchange of Pti,,SiH w i t h t r i t y l perch lo ra te , dnd as t h e

f r e e i o n i n tleCN o r su lpho lane u s i n g I 3 C o r I 5 N nmr spectrometry. P y r i d i n e

docs cotriplex w i t h Ph3Si+.208 Ozono lys is o f E tgS iH a t -7E°C g i v e s t h e ozon ide

which generates s i n g l e t oxygen on Jecoinposiny a t -6OoC. Whi le t r i h y d r i d o

p e n t a c o o r d i n a t e s i lanes have a low b a r r i e r t o i s o m e r i s a t i o n th rough

p s e u d o r o t a t i o n a t S i , d i h y d r i d e s s t a y e q u a t o r i a l , d n d a r e m a r k e d l y more

r e a c t i v e t h a n t e t r a c o o r d i n a t e spec ies as r e d u c i n g

(E t O I j S i H h y d r o s i l y l a t c s (E t0 I3S iCt1=CH2, 1,S-hexadien~ and rle2S i (CH=CH2l2,

t h e p r o d u c t s g i v i n g s i l a t r a n y l d e r i v a t i v e s w i t h t r i sa lcoho larn ines , whi Le

i n t r a m o l e c u l a r h y d r o s i L y l a t i o n o f a l l y 1 an0 h o m o a l l y l a lcoho ls , fo l lokec ! b y

o x i d a t i v e c l e a v a g e o f S i - C p r o v i d e s a new a p p r o a c h t o r e g i o c o n t r o l l e d

s y n t h e s i s o f 1,2- and 1,3-di0ls.~ '" p - t lydroxyketones a r e reduced t o

ant i -1,3-diols u s i n g Pr12SiHCl, w h i l e CF3S03ii/Et3SiH and a r y l ketones g i v e t h e

hydrocarbon.211 E s t e r s R'C02R w i t h Ph3SiH/But 2 2 0 a t 14OoC g i v e RH, w h i t e

IJafion-H c a t a l y s e d r e d u c t i o n o f a c e t a l s and k e t a l s by C , t 3 S i H g i ves e t h e r s

ArC1120Fln.212 Whi l e 2 - b e n t y l oximes g i v e t h e benzyloxyazane s t e r e o s p e c i f i c a l l y ,

R'R"C=NOH and Ph.SiH. y i e l d s t h e arninosi lane R'K"HCNHSiHPh2.213

CpLZrXz (X=Me,H) c a t a l y s e t h e dehydrogenat ive c o u p l i n g o f 1' and 2' s i lanes

t o g i v e d i s i Lanes, w h i l e PhSiH3 g i v e s C C p Z Z r ( S i i 4 2 P h ) ( ~ - ~ ) 3 2 i n s o l u t i o n , and

H S i l l o x i d a t i d c l y adds t o Fe(CO);PR'3 and R C (C0)LMn residues.214 The

k i n e t i c s o f base c a t a l y s e d s i l y l a t i o n of C O ~ ( C O ) ~ b y R j S i H suppor ts r a d i c a l

i n t e r m e d i a t e s n o t HCOCCO)~, a n d C O ~ ( C O ) ~ c a t a l y s e s t h e s y n t h e s i s o f t h e

s i loxymethy l idene y roup f r o m e s t e r s l s i lane/CO, and o f 1,4-disi Loxybutanes and

I - s i loxypropanes from ~ x e t a n e s . ~ " Rh(1) c a t a l y s e s t h e h y d r o s i l y l a t i o n o f

quinones, acetophenone and mono- and diaza-1,3-dienes ( t o N-si l y l a t e d

enaniines), w h i l e CpRh(C2H4)C0 a c t i v a t e s C-H and S i - l i bonds o n photod issoc ia -

t ion.216 H y d r o s i l y l a t i o n o f i s o p r e n e i n t h e presence o f Rh(1) o r Ru(I1) and

n i t r o g e n l i g a n d s as c o c a t a l y s t s o c c u r w i t h h i g h s t e r e o s p e c i f i c i t y , MenSiHCL3-n

L L

3 5 5

- -


( ~ = 1 , 2 > a d d s t o C, F, C i i = C i i 2 o r a l l y10C6F,3 i n t h e p r e s e n c e o f :i2PtC16,

t i y d r o t y s i s g i v i n c t t i e s i 1 o x a n t . ‘ l 7 c o t t s i c f o r r , i a t i o n i s shown t o be a n

e s s e n t i a l s t c p i n (COD)PtC12-catalysed h y d r c s i l y t a t i o n , IrH,(!;iEt3) (COD)L

r c i c t s w i t h C21 i4 B i v i n y b o t h E t 4 S i and EtgSiCH=CIi2, uh i Le R PAuCH. m e t h y l a t e s 3 3 t h e s i l a n e s HSi, izCl C3=Ke,Pti) and tiSiF;eCt2 w i t h o u t o x i d a t i v e a d d i t i o n . R 3 K i

(R=13u,Ph;f?=Si .Sd reduce a c e t y l r l ’ c o n l j l ~ x c s (l!’=Co,.i<ri) t o ace ta ldehyde and

J J

R ‘Y’ ( CO) xl.. 3” As w i t h H5Ge+, c i i l c u t a t i o n s i n d i c a t e ‘;IcGe;-l ’ cornprises H2 bonds-r.! on one 4

s i d e o f p l a n a r T.SBGe!i.,,+, Ph,Be3H and Ii,C=CtlCHX? (%=SCOSPP, S02p- to l ) g i v e a l l y l

and alkenytgermanes i n t h e presence o f Aitl;, and t h e h a l i d e s (CF,)EGeX4-1!

r rducec j w i t h I:aD1I4 o r :;a3D4. : C F 2 i n s e r t s t h e Ge-li bend."' i n FSb3d,

iie4-lSn:12 ( ~ = 1 - 4 ) r j i v e t h e c a t i o n s Ke- Sriti ’- a t -9iS°C, which decom~ose on rarmini ; t o i ‘ i e2~r i2+ an0 Sn2+, t h e e l e c t r o c h e m i c a l r e d u c t i o n o f Pi1 S n i i 2 and

Ph,SntiCL shoun t o g i v e Ph,SnH (011) ’- i n Sas ic met4 ia j whi It. tlePhSnCL2 and

ilcPhS nil, y i c LJ ur ist a b l e (ClF,?ePhS n) 2 .

Cu”..!;ntl has been u s e d i n t h e d e p r o t e c t i o n o f a l l y l and a l l y t o x y c a r b o r i y l

d e r i v a t i v e s o f amino acids, t h e r e d u c t i o n o f P-hydroxyketones, 2’ a l c o h o l s i n

t h e presence of t h i a z o l y l d i suL:,hi de,’” 5-suSst i t u t e t i u r i c i i nes, s t e r o i cjd L

h a l o h y d r i n s and esters, p r o d u c i n g 2’ a l c o h o l s f rom ketones, and d,lj-enones

from ol-ni:roketones,2’2 t o rec!uce t h i o h y d r o x a n i c es ters , i n t h e s y n t h e s i s o f

a romat ic steroic ‘s, and i n t h e Pd c a t d l y s e u f o r r l i y t a t i o n o f o r g a n i c h a t i d e s by

C0.223 h n 3 S n l l / A I f i N c o n v e r t g Lycosy l i s o t h i o c y a n a t e s t o 1,5-ai-ttiydro-D-a Id-

i tots , 2-a L k y l s u Lphony lbenzot h i a z o l e s t a t h e 2-s tanny l d e r i v a t i v e , r d l i c e

d c e t a t e s o f sc1!12 bronot iydr i r i s by a s t e r f o s p e c i f i c r a d i c a l rearrangement, and

c y c l i se bromoniet hy l s i l y Lpropa r g y t i c e t h e r s and hex-S-yny l i o d i c r ~ . . ~ ’ ~ The

s o l v e n t dependence of i i -abst r a c t i o n s f rom 3unlSn:i by t r i p l e t xanthoi ic i s

e x p t o r e d , t h e r a t e o f I l - a b s t r a c t i o n s b y PhCH

compared, and X / H exchangc stlown t o be f a s t between R X and :3un Snli i n t h e

presence o f Re(C0)4L’.

L 3

3-11 n 2

l- $3

o f PliSil and Run3Sntl(D) 2

3 225

5 R a d i c a l s and I o n i c D e r i v a t i v e s

Gas phase h o m o l y t i c s u b s t i t u t i o n by li a t S i i s f a s t i f o t h e r S i atoms a t t a c h e d

th rough a f a v o u r a b l e SOIIO, b u t - I Leads t o decreased r e a c t i v i t y . Me2SiHCHZ’

i s o n e r i s e s t o I le3Si ’ via a 1,2-H m i g r a t i o n and a 4 l k c a l / m o l . b a r r i e r (cd tc .

4 ~ ! - 6 ) , and t h e k i n e t i c s Of 12 / l le -S iBut show p-si s t a b i t i s a t i o n energy o f 12kJ

i n Me3SiClk2CH2’.226 S i L a c y c t o p e n t y l r a d i c a l s exchancje H o r D w i t h adaniantane

( o r C13D,6)

5

r e v e r s i b l y caus ing s p e c i f i c d e u t e r i a t i o n o r d e a e u t e r i a t i o n a t


> S i - I I o r >Si-0 bonds i n t h e r a d i c a l . S i l y t r a d i c a l s add t o u n s a t u r a t e d >CO

compounds r e y i o s e t e c t i v e l y , t h e n m d e r g o 1,3-C t o 0 s i L i c o i i a i g r a t i o n s , b u t

w i t h 2,6-i3ut2-p-benzoquinone, two s e t s of p r o d u c t s form, w i t h a d d i t i o n a t

oxygen or i n t h e r i n g . The i n t r a m o t e c u l a r r e a c t i o n o f a t k e n y t s i l y t r a d i c a l s . _

can be used t o e x p l a i n o t h e r second row r a d i c a l c y c l i s a t i o n ~ . ~ ~ ~ The r s r o f

c a t i o n r a d i c a l s o f s i t y l s u b s t i t u t e d e t h e r s and s u l p h i d e s s u p p o r t s a

c o n f i g u r a t i o n t o p r o v i d e f o r i n i x i n y S i - C # - o r b i t a l w i t h non-bonding ones o f 0

o r S . E x t e n s i v e a-x c o n j u g a t i o n i s a l s o founu i n s i t y t s u b s t i t u t e d benzeni! and

a t t y l s i l a n e c a t i o n C a l c u l a t i o n s sup i jo r t a s t r u c t u r e f o r

::e4Ge+, Ne (ie + i s 6 . IS-radicat b u t (f4e3G?)2X+ (X-3,Nli) a r e n - r a d i c a l s w h i t e

(Plr. tie)2Ct12 d i s s o c i a t e s t o f?e-Ge+ and X.:e3GeCH,' which i s p l a n a r a t t h e

r a d i c a l cen t re . (Ple,Cie) Y + (Y=O,S) have t r a n s - 9 l a n a r skeletons. ArCeEt3 and

PhZGeEt y i v e gerit iyt r d c i c a l s o n i r r a d i a t i o n , which add t o o t e f i n i c uoub l i i

S t a n n y l r a d i c a l s a r e yenerd tea by C-Sn anti Sn-Sn I-iomotysis, and f r o i t

atkyl,SnI, and a r e Less r e a c t i v e t h a n s i t y t o r d i s i l y t r a d i c a l s t o f i t r a n s f e r .

The r:dicaLs Ke,E4Ph2C' (K=C,Si,Ge,Sn) add 1,4- t o fI,C=C(CFi)SBut, t h e adducts

d i s s o c i a t i n g rev:rsibLy a t 2SoC, b u t 1,2- t o I12C=C(CIL)OSiRej (!-Mi).230

V a r i a b l e t e ? i , i p e r a t u r e 7 L i nmr shows t h e c o l l a p s e o f t h e L i s i a n a t f o r

Ph F?e3-nSiLi ( ~ = 1 - 3 ) i n THF, c y c l i c vot tdmmetry e s t a b l i s h e s t h e c o u p l i n g o f

b e n z o y t s i l a n e s t o 1,2-ilioL d e r i v s t i v e s , R t G C and P h k S i L i g i v e s b i s - s i t y t -

amino e thyne diri.er adducts, whi t e rlejSi- y i e l d s Me3SiO- and Ke3SiS- f rom t h e

>C=O and >C=S bonds.23' s i t y t c u p r a t e s y i v e a t l y t anci v i n y t s i t a n e s w i t t i a t t r n t - s

depending upon t h e subs t i t i Jen ts , whi Le w i t h 2' a l t y t acetates, e i t h e r enant iu -

mer o f an o p t i c a l l y a c t i v e d l t y t s i t a n c can be mad-? Frau a s i n g l e enatiorner o f

an o p t i c a l l y a c t i v e aL tyL a l c o h o l . Ac!Cition o f R C u t o +-unsaturated esters,

m i d e s , ketones and n i t r i t e s i s i iaproverl i n t h e presence o f Ze S i C L .

+ 2 5 5 '-

-I 2 2

n - z

232 3

Mg exchanges w i t h (rh?=,Sil Hr, i n t h e presence o f A? d(CH2)3 i~ l~4~2 t:, S i v e t h e

s i Cytmagnesiuci complex (Si-rig 2SS.lpm). S i l y t d i c r g d n o z i n c a t e s f,le2PhSiZnR2Li

undergo 1.4-adJi t i o n t o d,p-unsatu r a t ed ke tones f a s t e r t h a n t r ic r rQanoz i n c a t es,

and add t o a c e t y l e n e s G i v i n g v i n y t s i t a n e s w i t h h i y n s t e r e o and

r e g i ospeci f i c i t y . 233 Cross coup1 i rig (V!e,S i ) 31,41nr;$t4e w i t h a t k e n y l and a t t y t i c

s u t p h i d c s and Ythers Gives t h e s i lanes , rJhi Lc (Vie S i ) S i L i and aninoboranes

y i e t t i (F;e.Si).JiilifJit t h e n (rie3Si)3Sii3(oil)1 on hyc:roLysis.'" The nmr o f a

s e r i e s o f d L k y n y l ( s i t y t ) m e r c u r i a L s d r e i?xdminecl and t h e s t r u c t u r e of

(I4e Si1,M.i L i

2 2 2

3 3

5 d

- + (M=J,AL,Ga,In) ue termi r led by " L i ( ' , I ) ll.0.E.23s 3 2 3

L a s c r p h o t o t y s i s u f i'h I:?-, ~ ' 2 - g i v e s e v i ~ e n c ? d f t r i p l e t s t a t e - n 3-c i r 1 t e r : n e c i a t e s i n t h e d e c o m p o s i t i o n t o Phni4e3-nl;e' and S i L y t and s t a n n y l

r a d i c a l s fo r t t i s i t n i t a r l y , whi l e Ph l icLi g i v e s acytgerrnanes f rom e s t e r ~ . ~ ~ ' - -

3

104

Me Gefl (M=Li,Na,K) c l e a v e t h e d r y l - S n

and the m e r c u r i a l which i n t u r n was

Et2tieHBr and Pie3SiLi) .237 Ph3GeSbPh4

3


bond and (9:e3Si)EtZGeLi r e s u l t s f rom L i

formed from Et2Hg and Me3SiGeEt2H ( f r o m

r e s u l t s f rom (Ph3Ge)zf4 (F"I=Cd,Hg) and

Ph4SbCL, whi l e (CF3I3Ge- has C3v symmetry.238

The p e n t a c o o r d i n a t e s tannate complexes LiSnMe5-,Phn (PO-5) r e s u l t f roin

MeLi o r PhLi and t h e stannane. rJinr s u p p o r t s a t r i g o n a t - b i p y r a m i d a l s t r u c t u r e 239 u i t h Ph ap ica l , w i t h f4e S n and LiSnMe5 g i v i n g I l e coalescence on warming.

B u n 3 S n ~ i i s i n t e r m e d i a t e i n t h e p r e p a r a t i o n o f 6 - e t h o x y a l l y l stannanes,

s u b s t i t u t e d oxacyclohrxenes, end l , l -bisstannyLalkenes.240 A s e r i e s o f 2-, 3-, and 4-Me Sncyc tohexano ls r e s u l t f rom t h e cyclohexene epox iae and l le SnLi,

w t l i l e (ph Sn)2Zn.TlfDA adds t o a l k y n e s t o g i v e t h e v i r ~ y l s t a n n a n e . ~ ~ '

19e C Ta(SiPle3)CL3 (Ta-S i 266.9pm) r e s u l t s f r o m t h e t e t r a c h l o r i d e a n d

(ile S i ) Al .0Et2, c a n be m o n o s u b s t i t u t e d w i t h ROLi (R=r'ie S i o r But ) and 3 3 3 e l i m i n a t e s b?c.SiCL i n t h e preset ice o f l igan6s . W i t h CO, t h e u n s t a b l e

C:e5CgTsCL3('22-C3SiMe3) r e s u l t s , p y r i d i n e t h e n g i v i n g a z w i t t e r i o n i c adduct i n

which t h e p y r i d i n e i s r e p l a c a b l e try p h o ~ p h i n e s . ~ ~ ~ A s e r i e s o f mixed s i l y l -

t r a n s i t i o n m e t a l complexes sir,l-rG..i' have been made, C61i6Mn(C0)2 and :Lle3SiX g i v e

C H h?n(CO)2Silk3, whi Le d e p r o t o n a t i o n o f t&-Cp(CO)ZRe(SiPh3)H occurs a t C5H5

f o l l o w e d b y s i l y t m i g r a t i o n t o t h e r ing.243

I r r a d i a t i n g f.le C Fe(CO)2Sit4ej induces CU Loss, w i t h C2H4 i n s e r t i n y t h e

Fe-Si bond w i t h p - H t r a n s f e r t o g i v e tle C Fe(COIZH and v i n y l s i l a n e . T h i s p rov-

i d e s p r o o f o f a l l proposed s teps i n c d t a l y s e d h y d r o s i l y l a t i o n o f ole fin^.^^^ CpRhC ri o x i d a t i v e l y adds K S i i i , T:c C RhH2(SiEt3), e q u i l i b r a t e s w i t h C2t14 b o t h

p h o t o c h e m i c a l l y anc: thermal ly , whi l c t h e s t r u c t u r e o f r4e C I r H 2 ( S i E t 3 ) 2 sholrs

w ider ang les and l o n g e r bonri Lengths t t l d n t h e ::h cowplex.

A comparison of t h e gas phase r e a c t i v i t y o f (C0)5?:nM'Ph3 (li'=Si,iie,Sn)

shows an i n c r e a s e w i t h t h e s i z e of I.1' and w i t h CH t o be t h e most r e a c t i v e o f

t h e yases t r i e d ( w i t h i-C4Hl0,fJH H 1. CF TaH3 condenses 1:l w i t h MenSnClq-n

( ~ 3 - 2 needing E t ii f o r ~ 2 1 , t h a t f o r 5 1 showing Ta-Sn 275.?pm,

CyLHo(tI)SriirienCt3-n ( ~ = 0 - 3 ) arid Cp2Plo(Sn[4eZCL)2 r e s u l t s i m i l a r l y w i t h a l l Sn-?lo

bonds s h o r t <f s&le b y 20-33pm, and t r i s ( l - p y r a z o l y l ) m e t h y l g a L t a t e M o ( C O ) . - forms a Me-Sn d e r i ~ a t i v e . 2 ~ ' The s t r u c t u r e of HO~~(r-ti)~(CO)~~,(SitiPh~) and

O S . ( ~ - H ) ~ ( C O ) , ~ ( S ~ F I ~ ~ ) ~ g i v e 0 s - S i 245.5pm a n d 0s-Sn 272.6 and 209.Opm.

T r e a t i n s LnL. (OAc) CliL=(PhCO) CH I w i t h Ph3SnCl/Li/THF g i v e s L. LnSnPh.. (Ln=Y 2 2 2 L

o r Lanthanii 'e meta l ) w h i l e Cp3WEt2 and Ph S n t l g i v e t h e il-Sn d e r i v a t i v e s k i t h

3-Sn 3 1 5 . h p r i 1 . ~ ~ ~

4

3 3 3

5 5

3

-

5 6

5 5

5 5

2 4 3 5 s

343

4

3.2 2 - - 3

3 3

3

6 iii t r o y e n Compounds


The f i r s t t h e r m a l Ly s t a b l e i i - s i 1 y l d i v i : i y l a r l i r i e s r e s b l t on s i l y l a t i c n o f

2-ata-I,S-diencs, - ey. PhC(Et)=rlCPh=CHrle u s i n g tle3SiOS0,Cf3, and C f 3 S i C L 3 i s

p repared f o r t h e f i r s t tiine, f rom CF,SiH(I~lFie;l)L/ilCC o r as a s o l u t i o n frorn

S i C 1 4 and CF31ir/P(fEt2)3.245 3utPh 2 S i i r u t r c t s amines, l e a v i n g them s t a b l e t o

h y d r o l y s i s , a l k y l a t i o n and a c y l a t i o n , f4c3SiOCOCCL3 and Ph+ii g i v e Ph,:iSii?ej i n

:;ow y ie ld , i k s i L y l m a n i n e s used t o make enmides , and whi Le t i -s i l y l amides

g i v e s r y l a w i n e s w i t h A r L i , s i l y l l i t h i o an i ines a r t i i n t e r m e d i a t e i n t h e

prepa r d t i o n o f (acy lami no) n e t hani?boronat es .2'r9 S i L y 1 exchancp b e t m ? r i

Ke S i O CMe and Et3SiPlilRe i s catalysec! b y HCOWlie, w h i l e Me FiOSOzCF3 c d t a l y s e s

t h e s y n t h e s i s o f aminonethy la ted cc t rboxy l i c e s t e r s and a c i d s f row ke tcne s i l y l

a c e t a l s and (I.:r.,T,i),l,lCII=C(QSiKeJ)2 arid RCHP o r R,CO, vJhi l e E?r,SiiliiPh and

Tie S i O S O . C L z i v e PhhHSO Sil:e,, a u s e f u l p r e c u r s o r t; Ph6HZSJ3-.25r' (;Ft..Si).pH

s i l y l a t e s IICOidIlidhCOR t o g i v e CRC(OSiKe3)=N-12 w h i c h w i t h F- c y c l i s e s t o

3 1,5,4-oxadiazoles, and t h e p - 0 x 0 i ron(sa1en) i l imer t o g i v e Fe(sa1en)OSiFle

(FeOSi 142.7') .251

The s t r u c t u r e of We SiNMe., a t 116K shows n i t r o g e n s l i g h t l y non-planar u i t h

L

L L

3 2 3'

2 L

5 2 3 , 5

3 8 -

t l i e Si-N bond (171.9I~m) a l i t t l e l s t i g e r t h a n i n t h e vapour, t h a t o f s i l y l a t e d

e t h y l e n e diamit!. a t I N K t o have S i - i J 173.5pn, h h i l e CLH SiNfYie? i n t h e yils 252 phase i s monomeric (Si-:f lG.'3pr11), b u t a Gimer a t 1161: u i t h Si-N 1 E 1 . 4 ; m .

(PI) s i r d c 5 F 5 ) 2 c r y s t a l l i s e s -from c,ii w i t h 4 r i iotc.cu~es o f c r y s t a l l i s a t i o n arid

has S i - i i bond o f 175.5pir1, r h i l e ( P r 2Si:!Yut)2 (L) i s :gono- Qr d i p r o t o n a t e d a t

1.1 u s i n g AlCl../Cc,ti,4/CH2CL2, g i v i n y (LiH+AlCL4- and (L)H22+CL,ALOALCL-,L . I n

t h e l a t t e r , "N nmr shows fJ i n t h e q u a t e r n a r y r e y i o n anu t h e S;-I.J b o n 2 (179.2

p i n ) l o n g e r t h a n i n t h e unpro tonated r i n y (174.7pm) .253 C a l c u l a t i o n s s u p p o r t

more p-d X-bond ing i n c y c l o d i s i lazanes t h a n c y c l o s i Loxanes, and H2Si=NH t o

have a Low l i n e a r i s a t i o n b a r r i e r and t o be Less stab13 t h a n t h e s i l y l e n e

tlZH(~i)Si:.254 L i t h i a t i o n o f trleZSiHrJHR by 3ur'Li, f o l l o w e d by m e t h y l a t i o n o r

s i l y l a t i o n i n THF g i v e s t h e expec ted s u b s t i t u t i o n products, b u t i n rion-polar

solvents, t h e c y c l o s i lazanes for in as wel l , t h r o u y h t l i e s i Laimine i n t e r m e d i a t e

i.le 2 Si=idlt.255 (THF)3L iFFr i2S i=r~ChH2~ut3 hcts an Si-Pi bond o f 161.9pin and Si i !C of

172.1°, s u p p o r t i n g i i n i n o s i l a n e character, b u t r e a c t s u i t h k;e S i C l t o g i v e t h e

t h e c h l o r o analogue w i t h Si-1.1 164.9pm and Si8C 138.3', i n d i c a t i n g a m i n o s i l a n e

fea tures . H e a t i n g g i v e s t h e f r e e s i l a i m i n e and But.Si=NSiDut3 has Si-t.1 156.8pm

and S i f p C 177.8'. I r r a d i a t i n g Mes S i R 3 a t low T g i v e s t h e s i l a i m i n e FleszSi=Nles

which rear rdnges o n warming, w h i l e Mes (t4e S i ) S i P i 3 g i v e s Mes Si=i.iSiFie3 which

can be m a t r i x i s o l a t e d . 3 0 t h s i la i rn ines a r e yellow-orange.25b

The l i t h i a t c d a m i n o s i l a n e s ( D u t N L i ) 3 S i p h a n d ( a u t p i L i ) 2 S i r j e z a r e b o t h

d i m e r i c w i t t l t h e L i b and L i 4 u n i t s t r i g . a n t i p r i s m and b i s p h e n o i d r e s p e c t i v e l y ,

z

2 a, 4) 3,

3

L 3

2 3 2


w h i l e He6Si31J3H2Li.THF i s d i m e r i c w i t h a L i b r i d g e and s h o r t S i - N b o n d s

(1 69.7pm) a t t h e b r i dgehead. 257 (i-le3S i 21dLi induces s t e r e o s e l e c t i v e a Ldo l

condensat ion of R C I i O and n o r b o r n e n y l ketones, and i n TliF g i v e s t h e THF complex

as a d imer ( L i Cp-14 (S i Fie )23TIiF32, whi Le (BusMgCp-I.I (S i Me3) 21)2 JiSprOpOrt ion-

a t es t o 14gCrJ (S i Me3 1 212.

A s e r i e s o f cadmium amides C(R3Si)21J12Cd and t h e i r complexes (R=r.le) w i t h

amines have been examined. The s t r u c t u r e s o f C(Me3Si)-N12M (rl=Cd,Hg) show a

OZa s k e l e t o n f o r S i 2 1 V l i B i 2 i n t h e vapour phase.2h The s t r u c t u r e s o f

[ ( ~ l e ~ S i ) ~ t ~ l ~ M (M=Ce,Pr) show a non-planar skeleton, whi l e t h e d e r i v a t i v e s w i t h

H=Sm,Er,Y f a c i l i t a t e t h e e l k y l a t i o n o f q i o x i d e s t o g i v e RCHR'Cl120H ( f r o m

RCW a n d R ' L i ) as t h e d o m i n a t i n g i s o m e r , i n s h a r p c o n t r a s t t o R ' C U

reagents.

CpTiCLs induces decompos i t ion o f Me3Si lWJHSik3 t o N2, u h i Le t'ioOCL4 and

( I k - S i ) tJH o r (Me S i ) :JLi g i v e a m i x t u r e o f imicie and li2-rio complexes.

Cp W ( k-S)2(IJSil!e3)2 shous t h e S i n k ! a lmost l i n e a r (170.9°), w h i l e

CpFe(CO)LCPPhN(Sir.~e3)21 adds C F 3 C ~ C C F 3 t o g i v e a FePCiCCO ring.261 A s e r i e s of

n3-lJSifsie3 d e r i v a t i v e s o f t h e Co. c l u s t e r and (t:e S i ) 14 ones o f Co a r e

IJ3E can be used t o d i s t i n g u i s h t h e 5-coord ina te isomers o f

I:eIrlJ(Siiie2CH2PPh 1 X, t h e gerrnylene C(f4e3Si) 143 Ge: r e a c t s w i t h C ( C H ) Ir- fi-C112 t o b r i t i y e b o t h I r atoms, c o o r t i i n a t e monodentate, an6 o x i d a t i v e l y ado

CIj, t o I r f r o m Sit*le-. C(Ke S i ) I:l,Ulie s e l e c t i v e l y m e t h y l a t e s ketones. 3 2 2 i4e S i l l 3 s i l y l a t e s 1' and 2' a lcoho ls , and opens epox idcs r e g i o s e l e c t i v e l y 3

i n t h e presence o f T i ( 0 P r i l 4 o r Et20.BF3.264 The gas phase s t r u c t u r e s o f

17ezSiH(:lCX) (X=O,S) showed a s i n c l e cor i former w i t h tJCX e c l i p s i n g S i - H . The

isocyanate adds t o amino a l c o h o l s a t :AH2 and r e a c t i v i t y o f t h e S i and GE.

analogues of Id-neopentyl-iJ-ni t r o s o u r e a c ~ f i i p a r e d . ~ ' ~ Ii-lie S i - i r n i d a z o l r r e a c t s

w i t h e l e c t r o p h i L i c ile S i compounds via b i s - s i l y l i m i c a z o l i u m Ru and

Rh c a r h o n y l s c a t a l y s e t h e r i n g open ing o f (I:e2SiNii) b y H~ t o g i v e

o l i w s i lazanes, w h i l e condensing lFle2Si(NEt2l2 w i t h + a l k y l d i a m i n e s g i v e s t h e

b i s (1,3,2-oi a z a s i l a c y c L o a l k a n y l ) d i n e t hy l s i lane, and (RHLiS i l i e 2 ) w i t h MC l2

(M=Sn,Pb! g i v e t h e M(I1) h e t e r o c y c l e s as A n i t i n c s can be

p r o t e c t e d by i n c o r p o r a t i o n a s p a r t o f a 2,1,3-azadisi l a c y c l o p e n t a n e r ing,

w h i l e a s e r i e s o f s i l y l s u b s t i t u t e d o p t i c a l l y a c t i v e p - l a c t a n s have been

prepared.268 7 a n d 8 membered m i x e d s i l o x a t a n e s h a v e b e e n made a n d t h e

s o t v o l y s i s o f ?le6Si30(IJAr)2 shown t o b e two-s tep pseudo f i r s t o r d e r and t o be 269

f a s t e r t h a n t h a t o f t h e Si302NAr r i n g -

Atternpts t o make t h e R-N a l l e n e systern > & k C R 2 b y p y r o l y s i n g >U(F)CR SiKe3

was unsuccessful , b u t (R2N)2f3F and Bar3 d i d g i v e IF2k&h2 UF; (R=Me3Si and

2A

260

5 2 3 2

2 2 ) - 5 3 2

2 2 2 2 8 1 4 2

263

3 3

2


~ u ~ ) d t low temperature. Warming t o 25'C gave (Ile3Si1413Br)4.270 Condensing

ButMe2S i IJHlJLiS i Me2Uut u i t h (rle3S i 1 2tJBF2 y i ves the f luorobory 1 hydraz i ne whi ch

w i t h ButLi forms t he 3-membered diazaboracyclopropane w i t h exocyc l i c U-14 bonds

(140.6pm) sho r te r t han endocyc l ic ones by 2pm. The aminoborane Fh2Bl~(Out)Sillej

has a long B-N bond (143.3pm) and a no r rp lana r CpNCSi u n i t , wh i l e Rut2B1.1(tle)-

9-boraf luorene w i t h U< groups perpendicular, has 344 bonds o f 148.2pm and

139.2pm respectively.271 A se r ies o f bisborylamines r e s u l t from (F.;e3Sn)31J and

R2BCl, o r from (Ivie3Si)2fKX3utf41i2 and UuLi/ClDXY, H h i l e CLPXY g ives

lorylaminophosphi nes. Condensirig (1% S i )21JOIc,e and (f4e3Sn)2id14Me2 w i t h MeODC12

g ives the borazine, bu t w i t h PhCCl (Me3Si)2NOfle y i e l d s the 5-membered r i n g

dines, w i t h 3ut rJ(SnFle3)2, borazines form v i a stannylarni n o b o r ~ r i e s . ~ ~ ~ Coupling

>fiDClPHCEt3 w i t h (lir3Si)21itJa y i ves t h e >I!U=PR d e r i v a t i v e which d iner ises,

wh i l e > I S C 1 2 and ArP(Li)Sif4e3 g i v e t h e (BPI2 r i n y cri th LI-P bond 1 9 t p m . ~ ~ ~

While Cr le3Si (~ i ) r rJ2 and CC14, Car4 end Ile SiCC13 g i v e (Fie S i )2 i J - r J=C and

Ile-S i Il=;JS i Me3, o t he r or gani c p o l y ha 1 i cies y i e I d (f'le3S i t.1H 1 snd C I i C l3 forms

(ll:3S i 1 21 i - l i=C~4C I and t h e r i ng . 274 S i l y l a n i nophosp h i nes form z w i t t e r i ons

w i t h CS2, which themselves are methy lated by ReI. rye S i N 3 o x i c i s e s phosphines

t o R3P=l:SiFle3, which GeCl, and I ! C l 6 c leave a t Si-14, whi l e IJ-halosi lylphos-

phinimines r e s u l t from Du$iFlJH2 and PX5.275 The s t r u c t u r e of the >PIJ=PI+(R)P<

(R=lCe S i ) ske le ton i s Jeterminec' and the hindered phospha-Ill-azenc RP=NR'

(R=Bu ,R'=fle3Si) o imer ises by C2+1l c y c l o a d d i t i o n t o g i v e R'IJPAP(R)=IJR'.

Pie 3 Si(But)I:i;,(%)=i:But (X=S,Se) acids water, (DutNti)~P(X)OSil;e3 so formed

cornplexing w i t h PUCII) and P t ( I1 ) . Cyclophospha-V-azanes g i v e s p i r o compounds

v i t h (Re SiIzIJLi, as does t?PF4 w i t h ;i,O-bls-si Lyl-2-aniinophenol, wh i l e

I.le SiOr le and Me3SiNEt2 s u b s t i t u t e RNCP(0)F212, and >PCl cleaves s i l y l a t e d

ethylenediamine and (3-arninoethan01.~~' The es r spect ra o f C(I.le S i ) , f ~ l , " +

( ~ = 1 , 2 ) suggest i t t o decompose t o C(fle3Si)21.132P+. The adduct formed between

But!!JSille21iEutS)n: and Phg6-fH2 has a sho r t i n t ramo lecu la r H-bridge between 2 - C o f Ph and 14, thereby p r o v i d i n g a decomposit ion pathway t o

o-H4C6PPh2CHSnCHSnC61i4PPh2, which conta ins the (SnCHI2 square.277 - ( f J S C l ) 3 and I.;e3Sit!3 g i v e s (SNIx w h i l e ReCl4(tJS) ( t 4 S X I 2 - r e s u l t s f r o m

ReClc,(lJSC1), P O C l and (Me3SiNI2S ( X = C l ) and i s converted t o the bromide by

We3SiBr.278 A s e r i e s o f s i l y l s u b s t i t u t e d mixed BSII r i n g s r e s u l t from (rleB)2S3

and su lphur i ~ n i d e s . ~ ~ ~ ClS020H s u b s t i t u t e s N-si l y l i m i d a z o l e a t 14 b u t PhSeCl

s u b s t i t u t e s a t C4. U i t h aminosi lanes and N - s i l y l aaides, t he S e ( I I 1 amine I s

forracd, and d i s i l a z a n e s and SeOC12 g i v e (Me S i t 0 Se. ffe3SitJ(S02fle)2 has a long

Si-r.l bond (185.lpm)

3 - 2

Pli001!(SiMe3)B(Pli)~~Of:e, and w h i l e 6u r lt(SnKe2Br)2 and liUX g i v e d iazad ibo re t i -

3 3

3

1

i n

3

3

3

nn -

3

3 2


1,2,5-~zadigrrmazolidinss r e s u l t through double a d d i t i o n o f PhRtiellCL t o

scety lene on i r r a d i a t i o n fo l l owed by c y c l i s a t i o n w i t h MeKLiZ, and the

s t ruc tu res o f RtieH IJCS (R=Fle,CD3) determined and compared w i t h t h e i r

v i b r a t i o n a l spectra?" Srr14:i coupl ins i s observed i n Cy3SnNCS (1':OHz).

C a l c u l a t i o n s suggest s t r o n g Sn-Cl X -bond ing i n Me SnC14-r, (g=O-&) , b u t

e s s e n t i a l l y i o n i c bonding i n r-ie Sn(i;CS)4-E (:1=2,3). OU Z S n ( f i 3 2 1- and 3u?riCli.J 2 3 r e s u l t from Run2SnClZ and NaiJ-

The s t r u c t u r e o f 1 -aza-5-stanna-5-met hy 1 t r i c yc loC3.3.3.01 51 undeca ne shows

the t i n c o n f i g u r a t i o n in termediate between t r i g o n a l h ipyramidal and

te t rahedrs l , w i t h the Sn-!i d is tance o f 262.4pn, i n d i c a t i n g a donor-acceptor

i n t e r a c t i o n i n a t e t r a o r g a n o t i n compound.283 (Phl'le S i C H 1 S r r t r i a z o l e s are

tested a s acaricides, and whi le Pc i ( I1 ) cata lyses the aminat ion o f a r y l ha l i des

us ing Oun3Snf:Z

T i - C l e~chang??'~ (i-14eZNC6H4CHSi!:e3-C,rJ)methylphenyltin bromide i s c h i r a l a t

t i n , arid a se r ies o f phosphino thioformamide, amino acid, enamides, p y r a z o l y l

borate and p ipe raz ine b i s (d i th ioca rbamic1 a c i d complexes o f t i n The

n a t u r a l abundance ''N idt.lR spect ra o f a range 3f S i - N and Sn-TJ cotapouncis are

measured, and the r e l a t i o n s h i p es tab l i shed between the d i f f e r e n c e of the GcRLie

asymmetric and symmetric frequencies and the s i z e o f the r i n g i nco rpo ra t i ny

the group. 226

R 232

5'

2 2 3

( A r O ) T i C l , anti (We Sn) f,! gives the T i monoaniide through 2 2 3 3

7 Phosphorus, Arsenic, and Antimony Der i va t i ves

The f i r s t S i - P ( V ) compouncl has been made by monos i l y la t i ng (~-OC6H40)2PCl u i t h

(Me.Si)2Mg.DlE, wh i l e RP(SifC3)Li (R=2,4,6-But 3 6 2 C H 1 and Mcs2SiC12 g i v e the

phosphasi lene Mes2Si=PR bu t f o r R=But o r I-les, (f.le3Si)2SiC12 g i ves

g ives Et2N+(CH ) ?(SiMe3) (CH2)>, inethanolysis o f whictl i nd i ca tes opposi te

p o l a r i t y a t t he two P atoms, writh IleOP(CHZ)2PH(CH2)2 the product.''''3

S i ly lphosphines have been ex tens i ve l y used i n the synthes is o f P ( I I I )=C

der ivat ives.

(R=Me3Si,Ph,Pr'), (Me3Si)3P and c y c l i c 1,2-diacid ch lo r i oes g i ve 5-nembered P

heterocycles (except p h t h a l o y l d i c h l o r i d e which g ives the d i n e r through head-

head coupling).289 (Me,SiI3P w i t h oxazoliutn s a l t s i n thc presence of

KF/18-crown-6 g i v e 1,3-aza- and 1,2,4-diazaphospholes through oxa

substi tut ion.290 S i l y l , germyl, and s tanny l s u b s t i t u t e d a c y l phosphines have

been made, wh i l e CArP=C(OSiMe3)l2PCI ( A ~ = ~ , ~ , ~ - B U ~ ~ C ~ H ~ ) Loses CO, Me S i c 1 t o

g i ve ArP=P-C(OSiMe3)=PAr, t he f i r s t t riphosphabutadiene, a l so produced f rorn

3

RP(S iFlej)S i C L (S i l l e3 l2 only.2S7 l lydrophosphination o f ( v iny l I2P IE t2 by fle3SiPH 2 - 2 2

2,4,6-13ut C H P=C=O and ( P k 3 S i P R ) * g i v e CArP=C(OSille3)PR12 3 6 2

3


291 A rP= C (0s i Me3 1 P (S i Me3)

MesCsP=PC5Me5 can be s u b s t i t u t e d by RLi C R = B U ~ ( M ~ ~ S ~ ) N , ( M ~ ~ S ~ ) ~ X (X=N,CH)

and (Me3Sil3C1 t o g i ve RP=PC5Me5 and subsequently RP=PR. The e l e c t r o c h e d c a l

behaviour of C(tle3Si)3CP=PC(Si~e3)33' has been studied. ClP=C(Sif,lej)2 and

L i p (SiMe3)R g i v e the (P-phosphi nolmet hylenephosphi ne (R=8ut) o r diphosphene

(k=t)ut3C6H2)

r e s u l t from ArP(SiMe3)Li and C12f~lt1R2 (Fi=As,So).

(Me3SiI3P reac ts u i t h AdCOCl and A r C O C l t o g i ve t h e phosphyne RCEP. ArCzP

a l s o r e s u l t s from (Me3Si)2PLi, d rou te user! t o make ArCrAs from (Me3SiI2AsLi. 293 AdCrP forms 5 membered h e t e r o c y c l e s w i t h RC=h-Z, ButCH=N

(Me3SiI2PLi and CS2 g i v e the heterocyc le S(Me3Si)C=P-C(SSiMe3)P on s i l y l a t i o t i

w i t h Ke3SiC1, whi l e condensing ~-C(Me3Si)2P12Cg1i4 w i t h PhiGC=iiPh forms the

phosphayuanidi nu d e r i v a t i v e o f 1,2-Civtiosphi nobenzene and a

benzo-1,3-diphosphole.294

and A rPC 1 z .

through a P->C s i l y l m ig ra t i on . Phosphaarsenes and s t ibenes 29 2

and r,lerdg. I

@utC.ti FigBr and CLP=C(Ph)SiMe, gave k-3u C H P=C(Ph)SiMe which undergoes

C2+41 cyc loaddi t i on t o cyc lopentddiene. C lP=C (S il";e3I2 w i t h KLi (H=Me3Si CsC,

PhCzC, Ph) g ives R2PC(Si3e 1 P=C(SiMe3IZ, w i t h i n t ramo lecu la r c y c l o a d d i t i o n

s 4 t 6 4 3

3 2 occur r i ng f o r H=rle3SiCzC t o g i v e the cliphosphi rane, whi l e phosphabenzenes

295 r e s u l t from ClP=C(Si:k3)2 and rnethylsorbate o r 3-si loxy-1,3-butadiene.

(Me3Si)2C(Li)Cl crxidised RP=CR'R" (R',R"=Ph o r SiMe3) t o KPC=C(Sifle 1 l = C R ' R "

which rsarrangeu t o the phosphirane (R=Ph), whi Le CLPC=C(SiRe3)2J2 condenses

t o a bicycloC3.2.01 heterocyc le and i s reduced by Hg t o kiC(Sitle. 1 P=C(Sit3e3)-

S i ile2CH2PC=C (S iMe3) 212. 296 Me5C5P=C(Slfle 1 e x h i h i t s thermal ( E ) / ( Z )

i s o n i r r i s a t i o n o f the P=C double bond a t RT ('H t4MR) and i s cleaved a t P-C by

(MeCN)3F:(CO) t o g i ve tre5C5M( C0l3-P=C ( S i Me3)2 and thence

me C (C0)2M=P=C(Sineg)2, whi l e Cp(CO)2f~=P=C(SiMe3)~ ad& IleOH across both Mo=P

and P=C. Whi Le 2,4,6-ButC6H2P=C=0 and Ph3P=CHR g ive the ArP=C=CHR, Ph2C=C=0

3 2

5 2

3 27

5 5

and (I-le3Si)zPPh y i e l d i t s c y c l i c dimer, and condensing ArPCl and

L i (Me S i )C=C=CRH' g i ves l-phospha-1,2,3-butatrienes as ye l low l i qu ids . 2921 3

Condensing I I - S i C I Z w i t h LiPH and Li2PH y i ves an extens ive se r ies o f l i n e a r

and c y c l i c s i laphosphines, Cr(CO)4nbd induces d i sp ropor t i ona t ion o f

fle2SiPHSii~leZPSiile L PSi: lezPdil?e2 t o (rSe S i I 6 P 4 , a l s o produced from Li3P and

N e z l i C 1 2 PCPl: 2 3 S i ) P on warning.2" S u l p h u r o x i d i s e s p e r m e t h y l s i l y l

phosphines, (r?e,Si)4P2 and (fle3Si);P7 t o s i l y l thiophosphonates, phosphinates

and phosphates, wh i l e (Re3Si).,PR and PCL, condense t o g i ve d i and

t r i p h ~ s p h i n e s . ~ ~ ' P4(Si[:e3)3EUt a i d t rans -Pq(5~r~e3)~Uu tZ a re cleaved by RLi a t

the S i - P bond, wh i l e t&-P4(SiMe3)2aiJ Cfrom (Me3Si)2pP(SiPle )P(SiFle3)But atlc

; u tp~~Z ] , p4 (s i f l e3 )3 t~u t and p4(SiAej)4 are cleaved a t the P-P bond t o y i v e the

2

1

J

t 3


n-tetral jhosphides. These rear range arid d i s p r o p o r t i o n a t e o n warming t o 25OC t o

y i v e a v a r i e t y o f P d e r i v a t i v e s i n c l u d i n g Li3P7, and cyc lopenta and

cyc l o t r i phosph i ne s .3"0 (Ph3S i 1 3P7 occurs as enant i omorphs b u t (Ph3M) 3P7

(M=Ge,Sn) as racemates u h i l e ii3P7 ( fo rmed f rom (fle3c3il3P7 arid MeOH) occurs as

a m i x t u r e o f isomers.3o1 We3SiPPButPUut and lie9l-l g i v e Out2P,H which r i n g

eXpdndS t o aut3P4rl, whi le (F'te3Si)21JaP2, p r o v i d e s an example o f ';he f i r s t

p a r t i a l l y n e t a l l a t e d henicosaphosphi ne. CEut (Me3S i)P12BlJPr'2 anu

U

Pr'2;4BPButPSif4e3 have been mdde. 38 2 U

Re5C5 Fe(COI2P (S i [leg) g i v e s t h e s k e l e t o n s FeP=C(Mes)OS i Me3 w i t h MesCOC 1,

FeP=C(Ph)OSillej and FeP(COPh)* w i t h PhCOCl and F ~ P ( C S O U ~ ) ~ o n l y w i t h UutCOCL.

The Ru and 0s analogues behave s i m i l a r l y , w h i l e Li?R(SiMe3) a t t a c k s

Me5C5Re(CO) hot a t CO t o g i v e Me5C5Re(CO) (NO)C(OSiMe3)=PK th rough f,lejSi

migration.363 rle3SiPPh2 s u b s t i t u t e s Re(CO)5X t o g i v e (Ile SiPPh2)Rc(CO)4X wh ich

w i t h inore Re(CO)5X y i e l d s C(C0)4RePPh212. I'ln(C0) B r g i v e s t h e mixed product,

and HWn(C0)5 (R=Me,fle3SiCH ,Ph,Z-naphthyl) w i t h I:e SiPPh fo rms t h e 3 membered

r i n g (C0)4RtkR(OSif4e3)?Ph2 th rough i n s e r t i o n of Cu i n t o t h e bin-R bond, S i - 0

bond fo rmat i o n p r o v i d i rig an adui t i o n a 1 t hir!nochemi ca 1 ciri v i rig f orct? ."+ 4

phosphinomaleimiue complex o f ili C12 o x i L a t i v c l y couples (WejSi)2MPh (f<=P,As)

t o t h e UiPphPPh complax, Me SiPf leZ com2lexes Cp2TiC12, a d w h i l e A r X 3 o x i d d t i v e l y adds t o (PhjP)3Cofle, (Ph3P),CoSiXe3 and (Ph cietle,) Cork show low

r e a c t i v i ty.3L)5

The f i r s t c y c l o t r i p h o s p h i n o p h o s p l i i n e r e s u l t s :rom Eut?pOu ?Snt4e3 a n d

MePCL2, 5 - P h - 5 - p h o s ~ h ~ - 2 , S - ~ i t h i a - l - ~ t ~ ~ ~ ~ ~ ~ I r ) b i c ~ ~ l o ~ 3 . 3 . ~ 1 ~ 5 l o c t ~ n ~ shows d

Sn---P i n t e r a c t i o n o f 261pm and weak Sn---S i n t e r m o l e c u l a r i n t e r d c t i o l i s o f

331pm, whi le dut (P~I)P(CH2)3Snt4e~C12 shows a Sn---iJ i n t e r a c t i o n o f 3 0 7 . 8 p n 1 . ~ ~ '

P y r o l y s i n g I"k3SnP(CZF5)2 a t 3X!'C g i v e s F C P=C(F)CF, w h i l e CF As=CF, r e s u l t s

f rom Fie SnAs(CF3)2 a t ~ o O C . ~ ' ~ R C O C L s u b s t i t u t e s Cp;Cu)2FeAs(Siile I L t o y i v e

Cp(CO)2FeAs=C(OSil?e )R, w h i t e Me3SiAsR2 (R=fle,SiCIi2 o r F?es) w i t h GaCLr5 gave

(RLA~GaCL2)3, C (R2As)LGsCL12 and (it,As)-,Ga (&!Ps o n l y ) .sJz: f$e3SiSbP1es2 an3

( I le Si)2'3bf:cs r e s u l t f roin ?lg/ilr SiCI/i. les ShDr3-n(~1,2), and while o x i d i s i n g 3 3 (t4e3Si).SbPh s l o w l y i n a i o x a n g i v e s (PhSb), .dioxan, O2 gas g i v e s

PhSb (0s i rk3) .3i19

3 5

, 2 3 2

- ,*,

r

2 4 3

T

7 ,

5 z 3 L

5 3

3

L J

- - L U

3 Oxygen D e r i v a t i v e s

S i n g l e t - t r i p l e t s e p a r a t i o n f o r H S i = O a n d il S i = S i s l e s s t h a n t h a t f o r 2 2 formaldehyde, w h i l e u n i m o l e c u l a r d i s s o c i a t i o n of I.( Si=G g i v e s ti2 and S i = O v i d

HSi (0 i i ) .313 Suggesteu Fle2Si=0 s t r e t c h i n g f r q u e n c i e s f o r 29Si=3 anl; zpSi=lsO 2


a r e a t 1200-1210 a n d 1 1 6 2 - 1 1 7 4 ~ m - ~ ( forr : led f r o m Ne2SiHZ and 03), w h i l e 31 1

v i b r a t i ona 1 l y e x c i t ed Me3S i0 - decomposes th rough Me2S i =O as i nt ermedia te .

FVP o f I~c3SiSiMe(Of4e)Oal ly l g i v e s :S i (Ke>Oal ly l , which iso i i ie r i ses t o

R e ( a l l y l ) S i = o as t h e c y c l o t r i s i loxane i s observed, whi l e s p i r o c y c l o t r i s i L-

oxanes r e s u l t f rom a d i e p o x y s i l d s p i rononane and c y c l o s i loxanes thrcjugh t h e

i nt ermedi acy o f O=S i =O. 31 2

P r l Z S i (OH)* c o n s i s t s o f c y c l i c H-bonded d imers f u r t h e r L inked i n t o l a d d e r

c h a i n s and (HOSiPh2)Z0 shows 3 independent h y d r o x y s i l o x a n e molecu les i n t h e

l a t t i c e . 3 1 3 A c i d c a t a l y s e d condensat ion o f MFtZEi ( O H ) 2 i s eAplored, and T a f t a* cons tan t o f Me,SiO and p r o t o n a f f i n i t y o f I?e3SiOM measured (183.7kcal.,Iil l e s s

t h a n Whi le ( 5 i ~ ~ P h ~ S i ) ~ D shows S i - 0 bonds 163.5pm8 those o f

(HPh2Si)20 d i f f e r remarkab ly (156 arid 169pni), (~-0CNC6H4SifleR). 0 r e s u l t s f rom

r E r C ti iJ11- and A r L i c leaves (14e3Si) 0 g i v i n g ArOSiWe3, w h i l e t h e c a t a l y t i c - 6 4 2 2 a c t i v i t y o f Rh(1) s i l o x y a l k y l p h o s p h i n e complexes i s explored.315 M e s i t y l

s u b s t i t u t e d c y c l o d i s i loxanes show S i - S i c r o s s r i n g d i s t a n c e s s h o r t e r t h a n t h a t

of t h e S i - S i s i n y t e bod , and a c e t o l y s i s o f l-CL-l,3,S-f~e--3,5-(Me S iO)2cyc lo -

t r i s i loxane g i v e s a m i x t u r e of 3 isomers, t h a t i n Lowest c o n c e n t r a t i o t ) s i iowins

t h e l a r g e s t h i g h f i e l d s h i f t and h a v i n g an a 1 L - d c o n f i g ~ r a t i o n . ~ ' ~ A v a r i e t y

o f 3-meuSered h e t e r o c y c l e s have heen nade, n o t a b l y Si304M (M=Ge,P,As,Ti),

Si2Sn204 and S i . 0 CL, coup led c y c l u s i loxanes and s i l o ~ a n e / p h o s p h a z e n e s , ~ ~ ~

whi l e ur iusual con format ions r e s u l t f o r (3ut2SiOSii+?20)2 and (3utZSiOSiF.le2r.iH)2

w i t h b o t h a lmost planar, and t h e l a t t e r h a v i n g an almost l i n e a r SiOSi angle.

By co t i t rds t , (Pri2SiKil),, shows a tuti conforr.,JtiOr.i.318 CCp(CO),ieSi (tie) F120

shovs S i O S i t o 'st. l i n e a r , and an ex ter is iv t . rbnye of s u b s t i t u t e d iJolySi loxanes

made w i t h f u r i c t i o n a l groups t o h o l d t r a n s i t i o n w t a l catalysts,319 w h i l c

h y d r o l y s i n g CySiCL3 a f f o r d s Cy S i G g i v e s t h e

Z r s u b s t i t u t e d cube a s such s c a t a l y t i c ~ ~ ~ i i e t . ~ ~ ~ ~ C ~ ~ ~ r . ~ S i 0 ) 3 1 1 7 ~ g i v e s

13-d ike tone c o m p l e x e s and t h e " S i J E R s p e c t r a o f s i l y l a t e d s i l i c i c a c i d

I { -Kagadi te show 2 typr?s o f S i , c o r e and

The s t r u c t u r e s of s e v e r a l 1,3-dioxa-Z-si l a c y c l o a l k a n e s and t h e i r d imers a r e

determineo, s i l o x e r i c b r i d g e d he terocyc t t?s prcparcd, I,i:.fJ(sc:) ( c i i ) 0Sil;le o ( c H ~ ) ~

shows no t r a n s a n n u l a r Se---Si i n t e r a c t i o n (443.7pn1, and o-pheny lened ioxyd i -

n i e t h y l s i Lane shown t o be d i r n e r i ~ . ~ ~ ~ : j is(o-phenylenedioxy)SiR- i s reduced by

excess h y d r i d e s t 3 R S i i i j (R=Ph,l-naphthyt), R ' L i j i v e s R S i R ' g w h i l e

Si(g-0,C6H4)3 w i t h EtMyZr y i e l c s E t S i O C t i Oli-0. P s e u d o r o t a t i o n occurs f c r d i

and t r i f u n c t i o n a l ctimpouncis, b u t n o t nono (A6">23kcal.i;lol-1

i i y d r o l y t i c s t a b i l i t y o f s i l y l e t h e r s c o r r e l a t e s w i t h T a f t d va lues and i s

2

5 3

3 3

r h i c h w i t h Me C Zr(CH2Ph) 7 7 9 3

r 2 2 2

2-

3 h 4 y -323


d - d i ketones,

o x i d i s e s 1'

ketones. 325

Me,i-6 o x i d a t i v e l y c leaves I?Si14e(OEt)2 t o g i v e ROH w h i t e py2Cr0 3 a t k o x y s i Lanes t o aldehydes and (pyH+)2Cr20:- 2' a t k o x y s i Lanes t o

3 - L i t h i o f u r a n i s s i L o x y l a t e d a t p o s i t i o n 3 by (Me3Si)202, which

o x i d i s e s t h i o x a n e t o t h e S-oxide and n u c l e o s i d e p h o s p h i t e s t o phosphates.

4 2 ( r le3Si0)2P(0)C(CF~)20SiT?eg, (Fle3Si)20 coup les P(V) oxychtor idcs , Zri/Xe3SiCL

c o n v e r t s 2,2,2-tr ichtoroethoxy carbony t phosphonatcs t o s i l y l phosphi tes,

w h i l e t h e f i r s t s i l y L e t h e r s o f phosphorus o p t i c a t l y a c t i v e a t b o t h S i and ?

have !,een ma&.327 Phosph inoy l hydroxy tamines r e s u l t f rom p h o s p h i n i c c h l o r i d e s

and fale 3 SiO:uH2, wh ich Like Ne 3 Si0::1iSible3, r e s u l t s f roin ~ i 2 : ; C 1 1 2 C 1 i 2 N ! i 2 / t i 2 N ~ l l . ~ ~ ~ ~

w i t h t h e a G p r o p r i a t ? r a t i o o f f k 3 S i C l . ' 2 S 0-Si l y t a t e d cyanohydr ins a r e

i n t s r m e d i a t e s i n t h e p r e p a r a t i o n o f 2 - a m i n o a l c o h o l s and a c y t u i n s , w h i l e

0 - t r i w t h y l s i L y l o x i n e s can be IJ-alkylateci t o g i v e n i t r ~ n e s . ~ ' ~ CtSOZNtICOzS i i k3

i s used f o r nlaki ny t h i a t r i a z i ne d iux ides , 2,4,b-(f4e S i 0 ) - -1,3,5-t r i a z i ne

in te rmed i ; r te i n t h e p r e p a r a t i o n uf 2-azda l ten ium s a l t s , whi t e l - formamido- l -

(tle S iO)a lkenes r e s u t t from (f",e.,SiO) I J C H O and RZCU, and n i t r i t e s f rom b i s s i l y t

amiaes usincj f ~ u o r i d e . ~ ~ "

3 5

3 J 2

T h e du'?:e2Si g r o u p i s u s e d t o p r o t e c t i n t h e s y n t h e s i s o f m o r p h i n e ,

methynot ide f rom 0-glucose, (+)-ApLasndmycin, thronboxane 'd ano Ir7a-homotlirorn-

boxdne A, p r o s t a g l a n u i n F2 , ano i n carbapc.rie,n synthesis.331 Juti.'h,Si 9 r o t e c t s

Ll:i i n t h e p r e p d r a t i o n of t h e o p t i c a t t y p u r e TtiF f r d h n e n t o f a c y l t e t r o n i c a c i d

ionophore r:l3(:603, and s i t y l e t h e r s a r e c l e a n l y conver ted t o e s t e r s u s i n g a c i d

c h l o r i c i c s w i t h ZnC12/lleCi: c a t a l y s t . 3 3 2 Muti~le2SiCl/Et3t1 g r o v i d e s d r o u t e f o r

monosi t y t d t i o n O F l ,n-diots, DPJ c a t a l y s e s t h e t - t i ~ t y t . ~ i r n ~ t h y t s i t y l a t i o n o f iy

an6 Zy dtconuls, u h i l e h inorancc a t S i -0 i n vinyLi le-Si(I ,e,Si). .CSiI le20COCF 3 2 2 2

encouracjes nuc leoph i t i c a t t d c k a t >C=O, g i v i n z t h e s i tanot w i t h a z i d e and

cyanate, t i i l t n o t w i t h . fLuor ide ano t h i o c y d n a t e where S i -0 i s at tacked. Pr ' S i O

d o e s n o t d e p r e s s h i g h d i a s t e r e o m e r e x c e s s u s u a l t y f c u r l d f J r o t h r r d c n d

p l k o x y subs t i t u t i o n i n nuc 1 eoph i 1 i c add i t i on t o 2-ac y L-l,3-oxdt h i t ines

SiLyL t r i f t a t e s a r e used i n t h e / j - f u n c t i o n a l i s d t i o n o f c y c l i c enones and t o

conver t n i t r o a l k a n e s t o n i t r o s o a l k s n e a c e t d l s which p y r o t y s e t o s i Loxyoxi:ws,

t h e rearrangement o f d l t y t o x y a c e t a t e s , t h e removal o f €;ut:le S i u s i n l j E t do

cdm;iourds, whi 3bL2f%Si9SO,CF- g i v e s c s r b s x y t i c e s t e r s which r p s i s t

rec iuc t io r i by h y ~ i r i d o a t l l i n i n R t e s f ~ ~ ~ ~ S i t y i t r i f t d t e s a r e used i n i;Lycosiciatioi-i

o f snthracycLi : iones, and d e r i u a t i v e s o f Aiiip1ioteric;o 3.335 j -0 i ntcr l ,1cdidtes

o c c u r i n t h e s y r i t h c s i s o f (+)-Per iptanon 8 , p Z 2 ariu (+)-shtivene, whi L? (MeC),Si i s a p r e c u r s e r f o r t h e s y n t h e s i s a f s i t s analogues o f t r i p a r a n c l and

3

/-,-. ''

2 2

-t


2 t lieinox y t r i phet o 1, anii :assi s t s i n l'ii c hirc? t a i c l i t i ons . a -S i l o x ysu Lph i cics

(iiCHO/HZS/~le:ISiCL/py t h e n R ' L i ) a r e c lpavrc l 1,y K F t o s i v ? t h i o l s Z'Sl i , whi Le

RC(S)3Sirle3 and Z ~ ~ O C I o r ,JCS g i v e s a c y t s u t p h e n y l t ia l ic ies anti

I:iejSiCL/Ac20/HZSDl+ w i I t c l e a v e t h e C-0 uond o f S i Loxycyctopropanr

c d r b o x y l z t ~ s Give d- inc thy len t t -8 - I ru ty ro tac tones , a l k e n y l aLkoxys i lanes a r e

u x i d i s e d t o cX-hydroxyketones, and d c y t a t i o n of t?Li Ly csters/ f le- ,SiCL g i v e s

!wt , i i s i L y l k e t a l ~ . ~ ~ ' ' D i dnci t r i c h l o r o s i 1arit.s induce c o u p t i n y o f 1,i-ciikekonrs

t o p y r i l i u n s a l t s , and s i l y t a t e u c a r b o n n u c t e o p h i t e s c o u p l e w i t h k e t e r i e 5 ' F C ' d i t h i o a c t d l s . _'

s i t y t enoL t:tlcers a r e w i d e l y USCL: i r i s y r i t h e s i s , n o t a b l y t o ;;repare

h e t t! rocyctes, P-pl ieny 1 t h i o ketones, v i n y t t hioniuni ions, 8 - s i L y t a t e u a,/Q-unsat-

u r a t c u amides, c a r i j o x y t i c a c i d s and t h e L ieca t in system f rom f u r f u r y l l a c t u n e

c n o l ~ t e s , ~ ~ ~ se ler io s u b s t i t u t e d ketones, a z i r i d i n e s u s i n g If$, p - t r i i , i e t h y L s i L-

oxykrtones, o p t i c a 1 Ly a c t i v e d - s u l p h i n y t ketones, a l l y 1 m e t h y l cthers, 1:ichaeL

a d d u c t s u s i n 9 ~ u n s a t u r a t e d k e t o n e s , 5 - o x o c a r G o x y t i c s i c i d e s t e r s , and

d - s i l o x y pheny l s ~ l p h i d e s . ~ ~ ' The t 2 f f e c t s sf a c i d and t r i t y l s a l t s or! t h e

condensat ion be tkeen s i t y t enot e t h e r s and ECHO i s f u r t h e r examined, and base

used t o condense i ' - o x ~ b i c y c l o [ ~ . 2 . 1 l h ~ p t e n e s w i t h tle S i C L , anti p r e p a r c

d i a i e t h y l s i 1yL b is (enoL e t h e r s ) .342 13-Iodo s i l y l r n o l e t h e r s r e s u l t f rom t h e

a - c h t o r o o r 6-hromo k e t o n s s u s i n g i (oI / r l i?CN t h e n Vc S i C l , w h i l e ( P I ~ I L I ) ~

o x i d i s e s 1-r.k SiO-l-(2 ' - l le. S i O C 1-1 )ethc-ne t o 5-coumaranone and 2,2'-dihydroxy-

acetophenone.

S i L y l e r w l e t h e r s and PhNO y i e l d i soxazo l id ine-4 ,s -d iones whi lc . i s o x a z o t e s

r i n g ogen w i t h L3A, y i e l d i n g ( Z ) - P - s i l o x y a c r y l o n i t r i l e s w i t h l.ie3SiC1.344

I nt ram0 Le c u t a r r e a c t i sns o f ~ - I ~ P - , S i 0-2-v i ny t c yc Lop ropa ne

ca rboxy l a t e s p r o v i u'i: u s e f u 1 s y n t h e t i c i n t e rrneili a t e s and 2,3-di ctr l o r o - I ,4-

napl i thaqui rionf coup les w i t h s i L y l e n o l e t h e r s .345 3- (F1e3S i 0) a c r o t e i n w i t h RtIgX

p r o v i d e s a r o w t e t o (E ) - isomers o f d ,p -unsatura ted aldehydes, enoxys i l a w s

uscd t o make a c y c l i c 1,5-diketones, and i n f l u e n c e t h e c+/z r a t i o o f a l k y t a t i o t r

of I -C tJ -3 -Ar - l - (Me S i 0 ) a L l y l i c a n i o n s , a n d t h e s y n / a n t i r a t i o o f c h i r a L

U a c tone eno la t es . '" Ir, Pd, ano' P t c a t a t y s e t h e i s o n c r i s a t i c n o f

Me SiCH. COCH C L t o [I C=C(OSiMc )CHZCL, and t h e C3.3l-s igmdtropic rearrangement

o f s i t y t kc tene a c e t a t s o f l ~ l e - o l - ( a t l y l o x y ) a c e t a t e s p r o v i d e t h e f i r s t r e p o r t o f

such a n i ~ o i n e r i s a t i o n . ~ ~ ~

4 -

3

3

3 6 4 343

3 i e L s-A lcje r

3 2 2 2 3

S i loxy indenes add t o h e t e r o d i o n o p h i tes t o g i v e azaC13lannut?nes, 3 -s i l o x y

buta-1,3-dien-l-yL s u b s t i t u t e d g lucopyranos ides add t o bsnzoquinones as does

l-?4eO-l-Kc3sio bu tad ienes t o naphthaquinone t o y i v e a n t h r a q ~ i n o n e s . ~ ~ ~ A l l

t r a n s I - s i l o x y c o n j u y a t e d t r i e n e s auJ d i e n o p h i Les across C(3)-C(6) w h i l e t h e

Organometallic Chemistry 114

a l l c i s isoraer y i e l d s h e t e r o cyc tohexat l i rncs . 1,3,5-Tris(si Loxy)-l-I le3-l1rxir-

1,3,5-triens ( f ro l ; i i i i k e t o e s t c r s and LDA/Mc3SiCt) a c t s as a p - t r i c a r b o n y t

t r i a n i o n equ iva len t , cyc locondens ing t o benzene t r i o t s , w t i i t e t t i c cirjubte

i ' i ichaet a d d i t i o n o f s i l oxyd ienes y i e t i s d e c d t i n i l l k y t t h i o

s i toxy hta-1,3-dienes unckrl;o c y c t v s r o m a t i z a t i o n Ys inQ >C=g e t e c t r o v h i l e s ,

2 - s i Loxy-2,4-~jienes s e l e c t i v e l y prt:pareo', w h i t e t h e D i e t s - A l d e r r e d c t i o n o f

s i l o x y v i n y l a l t e n e s leads t o t h e s e s y u i t c r p c n e s dehydro fuk inone and

se t i na-lc (1 4 ) ,7 ( I I 1 -d i en-3-onr.

tJut t h e Prl ,Si arid 3utfie s i J c r i v a t y v e s & r e s t a b l e as t i l e yriot. (rGe3sidCG)2C2

d e c s r b o x y l a t e s t o I',e,SiCsCCO. Siiq?e3 i n Et3 f , w h i Lc s u t y h o n i c a c i d exchdtiye

r e s i n s can be usedJ t o 3 -aepro tec t b i s - s i t y t a t e d t e r i n i n a t a t k y n ~ t s . ~ ~ '

r)rcjanocopper(:) reagents c h a i n expant i K e - S i O d e r i v a t i v e s o f Z,3-liexauierr5-yn

1-01s t o 2,3,5-octat ritn-7-yn-1-01s anc; enones t o l - k - , S i 3-heyt-I-ciies.

The f l u o r o i s o p r o p e n y t e t h e r i f i c a t i o n of phenols r e s u l t s t l i rouytr

'l,5-bis(butRe. S iO)~rop-2-y t -Z ,5-J ich Loruhenzene sulphonate, PhCoCH 3 r g i v e s L z ?:lCC)Ci1LSiile3 v i a Plic(~Sif. lc;z)=CtILi, and t h e s t r u c t u r e o f

Ph,C=C(OS if;e,But)l,IPtiCO21.le shows i n t ra rao lccu tar if---S i i n t c r a c t ids3 w i t h u nb r i cigec WK

bonds, w h i l e (3U S i O ) la14 i r i s e r t s CO dnd C 2 i i 4 . i?eduLing (Dut3SiO) T a c t 2 w i t h

i id/Hg y i v e s (i3ut,SiO).-Tti which c l e a v e s CO and undcryoes s e t f c y c t o m e t a t l a t i o n

th rough C-H i r ~ : r r t i ; n . ~ ~ ~ The s i l o x i d e s ( U u t N ) 2 C r ( O S i C e ~ ) ~ i s r e a d i t y

d ry ta teu , w h i l e o x i d i s i n y (C3).t'lriCCCIi(Ph)OSirle, w i t l i rle h-6 g i v e s

suppor ts p-~l, x - b o n d i n y i n a t k o x y s i tanus jnci s i ~ o x a n e s . ~ ~ ~

7 ' 9

The y i io t c t h e r PhCH.,Ctl,CECOSiI~c.: isomt.riscfs i n THF/hexane t o X! ketene, L L

2

2

352

(Uu t3S i 0 ) M C 1. ( M=T a, ilb) a r e reduced t o K (bat 3S i 0 ) .,F,liI23

5 2 4

J 3 2

(CG)5HnCH (PhIQS i lk3 u h i ch pro tor la t e s t o iir-ln(CO) and CgH6. 3s' 2 9 s i idi.lR

C L S i (CH2CH2CM2)3:J hyclrolyses t o t l ie s j Loxarie which has an i n t r a r n o t e c u l a r

c e r t a i n conformat io r is i n s i tatranes, R 2 S i (OCH C H ),ill*tc! and

(Me3SiOCHZCH2)RiMe3-n, a l l c o n t s i n i n g t h e SiOCCli The o r i g i n o f

t h e s t i i e t d i n y e f f e c t i n 2 9 S i PJ!lR s p e c t r a o f s i l a t r d n e s and 1H-29Si c o u p l i n g

cons tan ts a r e d i c ~ s s e d , ~ ~ ' and t t ie s y n t h e s i s and s t r u c t u r e o f many

described.35Y A s e r i e s o f g r rmat ranes have been made and c a t c u t a t i o n s i n d i c a t e

t h a t i n t r a m o l e c u l a r bond ing i s s t r o n g e r f o r gt'r idatri lnes thzr i s i l a t r a n f ~ . ~ ~ '

K i n e t i c s and rilechanisrns o f iodo- anu m e r c u r i d e s t a n n y l a t i o n o f

pheny ts tannat ranes s u p p o r t s Sn-C f i s s i o n as t h e r a t e de termin ing

s i ---* IY ' bond o f 247.7ptn, w h i l e s p e c t r a suppor t th rough bond i n t e r a c t i o r i s w i t h

F 2 L

The d i s t o r t i o n observed i n v a r i o u s l y s u b s t i t u t e d s p i r o c y c l i c a n i o n i c m e t h y l

and pheny l g e m a n a t e s of s u b s t i t u t e d c a t a c h o l s and t h i o c a t a c h o l s i s e x p l a i n e d

b y L a t t i c e and e l e c t r o n i c e f fec ts .302 The epox ide Cti Gef,le C I I CHCHO e l i m i n a t e s -

2 2 2 u


2' :.lc2Ce=\) on FVP, C((:b3Si),l.;liGc(Oli)

g e r r a y l v n c s c y c l o add t o 3,5-i31; orthor;uinone, and t h e :LlR s p e c t r a o f

aLkoxyserni,nes i r i d i c d t e Less 1i-G %-!!c;nuinc t h a n i r : anatoguus a t k o x y s i Lcnes.363

:i Sn:: tx=olLy:,~li:,,hcllidc) c leaves o i t i ranes a n J oxeti!nes t o S i v e

x ( CH,) nRg, these i rise r t i n y i ; ' i; CS t o E i L e i soi9ie r i c 1, J- c;xa t h i o td rl-2- i n i nes

ano' 1,3-oxazolic' in-2-thirines ( ~ 3 1 , t h e i r r a t i o v a r y i n g w i t h I ? ' . ~ ~ '

I , . l - D i s u b s t i t u t c d c is tdnnoxdnes ar t ' used as t h u p t a t c s f o r uretl-idrlt. format ion,

l a c t o n i s a t i o n o f u -hydroxy c a r h o x y l i c a c i d s and t r s n s a t c c ~ h o t y s i s of c~sters.""

(cun-,Sn)2i) a n i C l C i i c i i NCU p r o v i d e t i l e i n t e r n c d i a t e f o r s u t - : s t i t u t c d Z-oAazot i -

c:i)ries, (Gun3Sn) o rcinovCs P ~ S srouj)s f r o n Plis s u b s t i t u t e d o t i g o r i b o n u c t e o - 2 t ides , i ind (~u".,Sn) Z / l l 0 / C r ( V I ) o x i d i s e s t i y d r o q u i n o l s 2nd naphthalene J i o t s

t o 1,4-qui nones.

2

r ? s i s t s dehydra t ion , u n l i k e Uut, tie(3H) tz 2

3

-

-: I

2 2

33662

C(Ft~.5i)2Ct11 Sn adds 1,4 t o I,+enones anri I ,Z -J ike t~r lcs , and e n a n t i o s l c r i c

p u r i f i c a t i o n throu! jh s e l f - d i s c r i m i n a t i o n i s found f o r t h e s y t i t h e s i s o f

c 8 i o x a s t a n n o l ~ t ~ e s f run HOC:I?CtI. 0:i u s i v g a c h i r a t d i b u t y t t i n reagents.

2,~- i~u"~-1 ,3 ,2- i ' ioxastannoldne Dccl l rs a s 6 r i a b o n p o t y l n i r i r l t h e s o t i d s t a t e

d i t h iriterrnoLr:cutLir Sn-0 bonds ( 2 5 1 p 1 ~ ~ ) l o n y e r t h a n those w i t h i n t i l e 5 r.rernbertd

r i n g (2J4pm). Or~,snostai i r iy ter Ic adducts circ' i.rscd i n t h e t o t a l s y n t h e s i s of

o c t o s y t a c i d A ( i s o t a t e t f ro in streptornyccs cacao i ) ."' tlut2bn(g Ci:), r e s u l t 2 - from !I;ut2Snu), and t h c c s r b o x y l i c and 3utG ii g i v e s t h e

p r r o x y starinane, which u i t h a l l y 1 a l c o h o l s g i v e s epoxicies w i t h h i g h r e 5 i o and

s t e r e o ~ e l c c t i v i t y . ~ ' ~ The f r e e r a d i c d l a d d i t i o n c f '.cuf'3Sn02CCti,f t o itCkenes on

warming w i t h AIUIJ i n v o l v e s i3un3SnOCd(CH2)2CiiB, therEt jy y i v i n y tactones, w h i l e

s i toxycyc lopropanes a r e r i n g opened by SnCL4 t o g i v e t h e p - c h l o r o s t a n n y l

ketories, s t a b i l i a e d by i n t r a m o l e c u l a r c o o r d i n a t i o n , i n good yield.-'73

R,Sn a c e t a t e s S ~ O W i i n i o n s e l e c t i v i t y a s pGtymeric membranes, o r g a n o t i n

a r y l o x y a c c t a t e s show i n t r a m o l e c u l a r O---r o n c o o r d i n a t i o n , w h i t e

t r i f l u o r o a c e t a t e s a r e d ~ s o c i a t e d . ' ~ ~ r l h ? SncOAc), i s monomeric w h i l e Cy Sn-3-

i n d o l y t a c e t a t e i s a s s o c i a t e d t h r o u g h +bonding, p r o v i d i n g t h e f i r s t example

o f a nonodentate c a r b o x y l a t e g roup bond ing t o tin.372 (Ph SnIZO w i t h 2- and

p-C1C61i4CO2H y i e l d PI1 S n ( ~ C t C n t 1 4 C 0 2 ) (1-3 polytner, Sri t r i g o n a l b i?yramidaL),

5 j 7 L

w h i t e (zu",SnU) L X 2

7 ,

z 3

3

3 - ( a l s o tri(:. b i p y . S n) a nci Ph3(g-ClC t i C i l - ) 6 4 L

(monameric, Sn-0 234.8 and 236.lpm1, Ph SnOCdAr a r c m a i n l y 4 coord ina te , r;e3Sn 3 e s t e r s of s a l i c y l i c and 9 - a n i s i c a c i d s o c c u r as c h a i n polymers, w h i l e w i t h

(Fie Sn),CJj, S n occurs i n d i f f e r e n t Sn atom s i t e s due t o t h e t r i c i i n t a t s n a t u r e

o f t h e cdr'bonate A s e r i e s o f o r g a n o t i n complexes o f l i - p r o t e c t e d

J i ,,ept i des, and 3 n i noca rbox y I i c a c i ds .374

3 L


9 Zulpt iur , Se len ium ani; T e l l u r i u r n D s r i v d t i v c s

C a l c u l a t i o n s i n c l i c a t c ?le2Si=S t o have 3si-s a t r jC!1-72Ccr1-~, u h i Le FVP of

s i l y l a t e d k c t v n e d i t h i o a c e t a l s p r o v i d e a r o u t e t o 17 C=C=S anc u s i n g a

br i t lgehead arltbrac+?nt? d e r i v a t i v e , p ropad iene t l i i o n e H C=C=C=S .57' P y r o l y s i n y

X,i3-f4e2-Y-si la-2,.5,4,5-S4bicycloC4.3.iJlnonane a t 43i!'C g i v e s m a i n l y t h e

s i lacycLogent?ne and t h e I - s i la-2-thiacyclohexa-S,S-diene, f rci-1 [le2!;i=S

a d d i t i o n t o i juta-l,z-diene, b u t a t L~X'C, CS2 anL: th iophene r e s u l t .

2-Si la-l,3-dithiacycLohexancz i s used as i n t e r i a e d i a t ? i r i t h e p r e p a r a t i o n of aldehyde 1,5-dithianes, w h i l e t i i i o s i Lanes a r e usei as t e r i ; i i n a t i o n groups f o r

p o l y m e r i s a t i o n o f a c r y l i c a c i d es ters , and PhSSi!le3 used t o make 3' a l k y l

pheny l s i r lph ides f roln n i t r ~ a l k a n e s . ~ ~ ' ' I2 o x i d i s e s :SePh,SiStJa t o t h e

u i s u l p h i d e whi Lc (i'kPh,Si)2Sn (@- lo ) have been prepared and used t o make

1-1 s 2 2 L I 1 '%cL

and (3uti)) S g H / E t - r \ : w i t h S i - S i bonds 233.bpm ( ~ ? , 3 ) and 2 3 4 . Y p ~ (~=4,micic'le

S i - S i bonds), w i t h S i - S 213.5pm.'"'

(Yip Si).,S i s r e a d i l y t r a n s s i l y l a t e d by R 2 S i C 1 2 and R S i C L 3 , and r e a c t s w i t h

2un2SnCl. and RP(S)CL2 t o g i v e (Eun SnS), and (APS2I2 . i . l ixed a l k o x y s i l t h i a n e s

and c y c l o s i l o x t h i a n e s r e s u l t o n t r a n s s i l y l a t i o n of (Tle3Si)2S, (CLi4ePhSi)ZS

c , i v ing (r,lePhSiOSiF4ePhS)2 i n good y i e l d , a s e r i e s o f S i s u b s t i t u t e d a l k y l e n e

d i t h i o p h o s p h a t e s made, and t h e new t r i c y c l i c U 3 N 4 S 2 S i z system ( w i t h i n t e r n a l

S->8 coordination) prepared f r o m PhB(IJHMe)2 and Me~UMeEI(Si,~eZCl)Si~ilC2CL.9;2

I - M e t h y l d i b e n z o s i lo le g i v e s t h e b i s s i to le s u l p h i d e a lmost q u a n t i t a t i v e l y w i t h

sulphur, has an S i S S i anc;ile of 108.8°, and forms a 1:l complex w i t h Cr(C0)6

th rough q ' - c o o r d i n a t i o n of one of t h e 6 membered r ings . Si-S i n t e r m e d i a t e s a r e

2

2

and D2sn on aLcohLotysis. ~ ( B u ~ o ) ~ S i S ~ ~ ( S i r q e . ) r e s u l t from cL(s i , t *

3 5 2 3

3 L

2 2 J

Group I V: The Silicon Group 117

used i n t h e s y n t h e s i s o f i3utiJ=V(SSiPh3I3 and VS (edt)ZZ-.3e3

I r r a d i a t i n g (FSes2GeI3 w i t h Ad=S g i v e s t h e 0. / H 0 s t a b l e g e r m a t h i i r a n e

d-S, w h i l e w i t h sulphur, t h e d i g e r m a t h i i r a n e r e s u l t s (Se a lso) . tiowever

R2Ge: (R=Fle,Ph) w i t h ButZC=C=S g i v e s t h e a l k y l i h n e d igcr rna th iane which

i n s e r t s 0 o r S i n t o t h e Ge-Ge bond.334 The d i t h i a p h o s p h a y e r m a t a n e anr!

digerrnolane ~(Gef:e,)nS~(S)C6ilq011?-e ( r ~ l . 2 ) p y r o l y s c t o (Ik2GeS)3 v i a - 2 Fle Ge=S

as in te rmed ia te , a c r y l i c and v i n y l compounck add HGeC13, i-I$ t h e n y i e l d i n g

(RCeI4S6 w h i c h shows a n t i t u r n o u r a n d ~ n a l y e s i c a c t i v i t y . 3 8 5 k s e r i e s o f

d i t h i o c a r b a m a t e d e r i v a t i v e s o f Ge habe been :nac!e, a l c n g w i t h b i o a c t i v e

t r i t h i agermat r a m s .356

The c o n f o r m a t i o n of Ilc-.SnSPh i n t h e g a s p h a s e i s d e t e r m i n e d b y U‘iPE

spectroscopy, c y c l i c d i s u t p h i d e s r e s u l t from o x i d i s i n g 3un SnS (CIi2)nSSnBu”3

u s i n g I /dr2, whi tc Ci4e2(PhS)Sn32 a s s i s t s t h e p h o t o l y t i c r e d u c t i v e c o u p l i n g o f

a r y t ketones t o 1:inacols t h r o u g h l,5,2-dioxastannotane f o r m a t i o n and

e t i n i i n a t i o n o f Ik,Sn(SPh)L.387 (But2SnS l 2 g i v e s Dut3SnSLi u i t h “DutLi,

h y d r o l y s i s g i v i n g t h e f i r s t s t a b l e t i n t h i o l , u h i c h w i t h l,ie.Sntil;e2 f o m s t h e

mixed su lph ide . ?:Xi c leaves Ph SnCSC(S)RI t o g i v s ;?C(S)SSr.

Ph3SnSZCOPri shows S,D-xanthate c o o r d i n a t i o n ($in---<) 2Y5.clpm). Sn-C

couj;ling cons tan ts f o r R Sn(S,COR’)2 s u p p o r t s t e t r a h e d r a l s t r u c t u r e a t Sn, and

s o l i d s t a t e I 3 C X I i R s p e c t r a r e p o r t e d f o r (He SnSI3, F:e2Sn(S,CNEt2)2 and

Ph Snlle ( two I*?€ resonances!) .”’ A s e r i p s o f RSn t r i s ( Z i t h i c . p h 0 ~ ~ h a t c . s ) ! lave

b e e n made, R2Sn(14) (Ct{2)ZPHPh and I$e,Sn(Cil. 1 PI!Ph o x i d i s e d b y S u l p h u r t o

c r i th iop l iosvh ina tes d h i c h complex w i t h HMPA, L r t i i l e : ’~‘- ‘ZSnCSP(S)32C2iie,~ i s

monomeric w i t h a d i s t o r t c ~ o c t a h e d r a l s t r u c t u r ~ . ~ ” ) CF,le.,Sri(S t l )I2 *s ivus

Pt(S2X21i) (Pt:e3l2+ w i t h c&-PtCL,(Pr?ej)Z 2nd (I? 3 rlS)2Fe2(CO):, coriipleses

(r:=Sn,Pb) have been

Se lenos i Lanes have been prepared f ro4 Ar2r/?:z/Se and Me SiCL, and f r o m

Ke.SiSet:a and Iy a l k y l bromides o r PhCHZQr, b u t n o t 2’ i)r 5’ ones, t h e r e i s no

t r a n s a n n u l a r S i - - -Se i n t e r a c t i o n (44.i.7pn) i n OSirie,G(Cli ) Prle(Se) ( ~ i ( . ) ‘ 2 2 c 2’ u h i l e Me. SiTePh and H C O C l forta t e t l u r o t e s t e r s R C O T P P ~ . ~ ’ ~

2 2

3

2

322 2 L

2 L 2

3

J 2 3

c 2 2

3

5 I

3

li3 Halogen D e r i v a t i v e s


2 i n t o bone, u h i t e g a s Ghsse s t r u c t u r e s o f Me4-nSiF

i n d i c a t e l i t t l c p-d X - b o n d i n g i f c o n t r a c t i o n o f t h e va lence s h e l l w i t h F

s u b s t i t u t i o n i s considered. For f.le3SiX, Id, I 3 C anti 3 S i Nf-T s p e c t r a suppor ts

b e t t e r p-d r - b o n d i n g f o r 0 t h a n II o r CL.395 A s e r i e s o f s t e r i c a l l y crowded

d i f l u o r o s i l a n e s have Seen made, g i v i n g an o r d e r o f b u l k i n e s s such t h a t

Tsi=2,4,6-0ut C t i >2,4,6-Pri. C Il,>i%ut>r)es>PriX t X l e . Organof l u o r o s i Lanes and

R S i F5- a r e assessed as o r g a n y l a t i n g agents, whi l e (13-croun-6)K’ coniplexes o f

PhnSiF5-,,- ( r ~ 1 - 3 ) dnd tlePhSiF,- a r e n o n - h y ~ r o s c o p i c . ~ ~ ~ I n t h e presence o f

I , t4e S i c 1 reduces t h i o s u l p h o n a t e s RS02SR’ t o t h e d isu lph ide , c y c l o p r o p y l

a l c o h o l s a r e c o n v e r t e d t o t h e h a l i d e s w i t h 14e,SiCI/LiX (X=Or,I), w h i l e w i t h

p;psSi I, tetrachtorocyclopropem gives the f i r s t i o n i c cdrljon halido, explosive

C. I ‘I-, t h e c a t i o n o f which can L:? l i a r n i n a t e d L:y l&7SilXle

- fac-(CF3I3GeF:- and ,c&-(CF~)~GCF;~-, whi Lr t h e s o l u t i o n s t r u c t u r e o f Ph 3 Gc3r

(among o t h e r a r y l ycr:nanes) d i f f e r s f rom t h a t of: the The hor i iotyt ic

s u b s t i t u t i o n o f K S n l ! ~ y I ’ i s studieb, w h i l e 3un,SnT/base c a t a l y s e s

t ie t r rocumi lene c y c t o a d d i t i o n t o o x i S t r u c t u r s d d e t e r m i n a t i o n s of

Cy2SnX2 (X=Cl,3r) dnd !.leSn13 show d i s c r e t e t e t r a h d r a l mo lecu les t d i tli s m e

r a u t t i p l e bond c h a r a c t e r suggested f o r ~ n - 1 . ~ ” R c f r a c t i v i t i 2 s o f Me SnX4,,

show r e g u l a r t r e n d s t h r o u y h S i , Ge, and S n u h i l e t c t r d t h i a f u t v a l e n e arid

te t raseLonafuLvdLcne s d l t s o f l?2SnCL4 ( R = t t,Ph) behave as s e r ~ i i c o n t l u c t o r s . ~ ~ ”

Crown r?ther Complexes o f 2 S n X 2 (X=C104,ilCS) have bt:en prepared and a t t are1

thought t o possess o c t a h e d r a l gcometry, w h i l e (~i::)RC=S=O.SrlCl~flc - “ ? i s

a s s o c i a t e d t h r o u g h weak in tc .nno lacuLar C t - L r i d y e ~ . ~ ‘ ] ~ ;lie s t r u c t u r e , s p c c t r a

and s o l u t i o n p r o p e r t i e s o f o r g a n o t i n (and Lead) h a t i w s i n t h e presence o f

I-IMPT,~” Ph3P3 dnu DlTS94a* a r e e x t e n s i v e l y s t u d i e d . The MeSnf!2 a n g l e i s

r e l a t e d t o Sn-ti c o u p l i n g cons tan ts t h r o u g h a smooth

(n=1-3) and iJutzSiF

3 6 4 3 5 1-

-3 4

397 5 3 2 2‘ -

( C F . ),(;ex (X=halogcn) o r (CF,)4Gs d i t h F- s i v e (CF3)3GeF2 ( F a i t i d t ) , 5 ,

3

2-

2

-l I

11 Complexes

T h i s s e c t i o n L i s t s complexes by J o u r n a l r e f c r c n c e o n l y . S i and Sn S c h i f f

ci iamines o f b i d e n t a t e ri---~ c o o r i i n a t e d , t : ider i td te ti---s

and t r i d e r i t a t e t;---S---O cocrdinatt?G,4‘13 and d i k e t o OrganoSi-,

be-, an(: S n - t r a n s i t i o n m e t a l d e r i v a t i v e s a r e i n c l u d e d i n s e c t i o n S .

4 3 ‘1


;<ef i ' re ric F-s

1

2

L.A.PaqiJette, m. ;!pv. I?:.:S,. 86, 733; T.A.i:Luinenkopf and L.E.Ovcrman, - ibid, Y57; E.Vitd?js and F.rj.::est, - ibicl, Y41; P.Jutzi, u, FS3. :J.Beschler, P.KLeinschnidt, and P.PanstEr, Ansew. Chem. Inn. Etf. w., 1986, 25, 236. Orc,anosi t i c o n & Sio-orzdnosi L icon Cbmist ry , Ed. H.Sakurai, E l l i s llorwood Ltd., 19% (Che,?. &., 13J5, 104, 11!37:!3 t o 109715, 12~9412 t o li13c14t~ snc! 1:+:359 t o 143?4?); E.Colon~r , :3utlL. z. Catalana Cienc. e., Quim. x. 7935, 4, 215 (Cher;,. AJs., 1946, 105, 17?532). Actual. x., 19?L, 5-R2(Cheln. A&., IXX, 105, 78972. and 77517 t o 975%2), S . 2 . Futschmann, S i l i c o n i n 3r2anic Synthesis. Pd r t s 11 and 12 SLZ, Scllueiz. Lah.2. 17C5, 42, LC'3 ant! 24P (Cliaa. A!>s., IT%, 104, 143932

-- _I___

-

- - -- -- dtld 1:dS23).

5 h.ci$bwnstein and F.L'.iam,rc, Xcv. Ctle,i. Interiacw. 1?M, 6, 775 (Chern. s., 1 3 ~ 6 , 104, 9751 5 1 ; T o j i c s i n x r ren t C hcmi s t r y , S I., r i nye r-Ve r L a g T J u , 131, 1 and 03; A.Condoni, Lcc t . ! ictkrOcycl. Chen. 1355, 8, 13 (m. ASS., 1936, 1C4, 102517). -

6 Phosphorus Sulphur, 1385, 27, 1, 43, 211, 65, anc 26, 327. 7 C.-s.Liu and T.-l.tlwang, =. Inorg. Radiochori., t c A . ll.J.Emolcus anu

.rl.u.Sharrt,, 4cdci?nic Press, 1025, 29, 1; S.IJ.tIg and J.J .ZuckPrman, ibiif, 237; A.6.Drook and K.::.Oaincs, ncfv. Srcanoiiet. Chern., Ed. F.G.A.Stone and R.\lest, Acacernic Press , lY?$), 25, 1 and P.Jutzi,il,id, IBLi, 26, 217; A.tI.Couley and N.C.Normdn, Progress i n Inorc,. Chem., Ed. S.J .Lippard, In tcrsc ienc?, 1986, 34, 1. Revierrs o f S i l i con , Cicrtiidnium, %, and Lea6 Conpouncs, Frwnd, TeL Aviv, 1935, 8, 219, 157, 135, 291, 171. Revi2us o f S i l i con , Geriaaniun, Tin, and Lead Conpounds, Freunl, T e l Aviv, 1985, 8, 237, 169 and 313, 263, 327 and 363. S.S.Davies, S .E.Thonas, and P.F.Gordun, g . Syttth. rl?tho(;s, IF&, 8, 512; ~.Rertrand,, J.-P.fldjora1, and A.aaceiredo, fi. z. E., 1936, 19, 17; CoinmPnts on I n j r y a n i c Chemistry, 1986, V, 247 am: 231. T.N.Mitchel1, J. Organonet. x., 1986, 304, I; J.K.Stille, Myeu. m. - Int. g. F - n g l . , 1386, 25, 50.7; G.K.Sandhu and K.YaL'av, J. G. x., 1954, 10, 31 (E. E., 1906, 104, 2GS963); G.Wrackineyer, Annu. Rep. l i l lR Spectrosc., 1985, 16, 73 (m. E., 1980, 104, 12934E). A.S.Drook, 1. Organomet. a., 1986, MU, 21; W.A.G.Graham, z, 31; R.West, m, 327. Oryanonrtal t i c Chemistry Reviews; Annual ';urveys (J-. Oryanonet. 5. L i b r a r y ) Ed. K.B.!:ing and J.P.CLiver, E l sev ier , 1955; G.L.Larsen, J. Orydnomet. m., 1926, 313, 141; J.Y.Corey, c, 1; J.Wolters and D.de VOS, w, 413. S.Pawlenko, Oryanosi L icon Chemistry, de Cryyter, 1985; Gmelin HandSook of Inorganic Chemistry, 8 t h Ed i t i on , System S i - C . S i l i c o n Carbide, 19% and Sn-Organot i n Compounds, Pa r t 12. T r i propy 1 t in- and T r i b u t y l t in-Oxygen compounds, 1985; Chemistry Source Books, Organometal l ic Compounds of Si l i con , Co. D.R.M.Walton, Chapnan and H a l l , 1955 and Oryanoneta l l ic Compounds o f Gc, z, and Pb, Ed. P.G.Harrison.

15 (a) Orgsnometal l ic Syntheses, Ed. R.B.King and J.J.Eisch, E l s e v i e r 3, 1086 (b) Inorg i in ic Syntheses, 1335, 24, 89, 92, 94, 110, 117, 120 and 1985, 23, 21 (c ) Organic Syntheses, 19D0, 64, 221 and 1.32. (a) m. E., 1986, 104, 109704, 1615522, 168525 and m. k., 1986, 105, 7896Y (h) =. &., 19S6, 104, 163515 and 136471 ( c l e. %., 1936, 104, 53303, 172527, 224923.

1986, 105, 172564); A.Sekiguchi and W.Ando, z. s., 1 9 ~ 2 0 ~ M.-H.YPh, L.Linder, D.Y.Hoffman, and T.J.Uarton, J. Amer. Chem. g., 1985, 108, 7249; P.R.Jones, T.F.Bates, X.F.Cowley7 and A . M . R r i f , -, 3122. il.Wiberg and B.Wagnrr, c. z., 1986, 119, 1455 2nd 1467. IJ.Wibet-9, K.Schurz, and G.Fischer, m. z., I Y J G , 119, 3433; IJ.Wiberg

t

9

1U

-- 11

12

13

14

I 6

17 S.Sakai and M.S.Gordon, Chem. Phys. Lett., 1986, 123, 405 (Chcm. Abs.,

18 19


and tl.Kopf, J. Urcja1ior:ret. Chen., 19&6, 315, (1. 2fl t!.i,!iberg and C.-t;.Liii~, %. = . e 1926, 119, 29% and 2330; K.D.DobLs anti

!:.J.ilehrt?, i ) rganorwta lL ics , 1986, 5 , 2!!!57. 21 ':.<.Shin mtl J.L.Ceaurnont, I. ?liys. Chcm., I ' > X , 90, 1507; it.W.Frey,

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23 i<.S.Srev 2nd ii.F.Schaefcr 111, 1. Amcr. Chem. K., 1926, ld8, 5204; C;.Kaabe, H.Vancik, R.West, and J.MichL, E, 671; R.T.ConLin arid Y.-W.Kwak, -, ,":34.

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29 H.Schumann, I .Albrecht, J.LoLeL, i .iiahn, M.D.iior,sain, and R. van d e r tielm, Orpanomcta l l i cs , 1736, 5, 1294; I:.J .Evans, %.Dominguez, and T.f'.aanusa, i b i d, 1291 ; r1.H. Chi sho lm, 2 .U.E i c h horn, K . Fo l t i ny, J . C .i luf f maim, and ii.J.Tatz, E, 1593; P.A.ShapLay, Z.-Y.ilun, anci J.C.tIuffman, -, 12:)9; J.Z.Cayias, E.A.Oabaian, D.C.;lrncir, S.G.Bott, and J.L.AtwooJ, J. %. S O C . , D a l t o n Trans., 1936, 2743.

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19db, 25, 1111; P.Hornbach, I l . t l i ldenbrand, H.Pritzkow, and t:.Siebert, i h i d , 1112.

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22

2& k.>ainraucr, C.i~.~epiJy, I.Fi.T.Davidson, and K.J.Hughes, Organometat l ics,

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26

27

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31 ti.Schmidt, G.E!aun, L.;:assa, and A.Derndt, Anyew. Chen. a. 3. Engl.,

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33 N.S.Hosmane, P.de Fleester, :J.I4.MaLdar, S.B.Potts, S.S.C.Chu, and

54

35 R.Yoneda, K.Santo, S .Harusawa, and T.Kurihara, Synthes is , 1336, 1054;


36

37

33

39 4 0

41

42

43

44

45

46

47

4 9

43

5il

5 1

52

53

5 4

55

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Ii.H.Karsch, A.AppeLt, and ti.!lariika, J. OrGanoinet. =., I'X5, 312, C1; H. H . Ka rsch, 4. Ap,x L t , and G. I. lul l e r , 0 rganometa 1 Li cs, 1W6, 5, 1504; A.L.Uzlch anc D.E.;)ram, E, 2159 . i1.ll.Karsch and A.Appelt, J. Organornzt. Chcm., 13%, 312, C6; E.Jurkschat, il.-P.Abicht, A.Tzschach, and B.flahieu, E, 309, C47. R.L.Wells, A.P.Purdy, A.T.FlcPhaiL, and C.G.Pitt, J . Oryanonst. -., 1936, 308, 2L;l an6 J. a. E., Chem. Commun.,-l9- :;.E.SchelLr.r, S.Iwasaki, and S.Fre i# w. Chim. M, 13%, 69, 7373; i i.ZiLch arid R.Tacke, J . Organumet. Ctiem., I= 316, 26,; 1.t:atsuda d n i S.Sato, ijid, 314, 47: T.Flakajinld, fl.Tanabe, K.Ohno, R.Ser;i, 2nd S.Suga, Ciien. L u t t ., I?%, 177; A.E.ScheLler and 3.Frei, He lv . Chin. Acta, 19815, 69, 44; T.f.lakajinia, l+.Viyaj i , P??.Scc;i, and S.Suga, Cheiii. L e t t ., 1986, 181. T.irenneche, M.L.Christidnsen, and K.Undheir~, Acta Chein. Scdrd., Ser.D, I?%, 40, 730; Li.i)ppoLzer, ii.J.T.li LLs, !d.Pachinger, ano T.Stevensun, c. -- Chim. Acta, 191;6, 69, 1542; J.D.Nies, J.II.DeLlslna, and t:.:3cn-Zi/i, InOrcJ. - Chi::). E, 1926, 118, I. D.Terununa, K.;Cato, M.Kamai, H.Uchida, S .Ucno, and Il. iwhira, n u l l . Chew. - - SOC. Jpn., 1986, 59, 3561; R.:3ellassoued, J .-E .Dubois, drid E . ikr tounesque, Te t rahedron E., 1786, 27, 2623; it.F.Cunico, G, 4253. E .E .ASoujaoudc, S . L i e t j e , N.CoLLiynon, rr.P.Teulade, arid r.Savignac, Syhthesis, 13iX, 934; J.i3inder and E.Zbi rat , Te t rahedron E., I'Xh, 27,

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-

5229 .

122 Organometallic Chemhtry

5 5 H.TJishiyama, M.~?atsumoto, H.Arai, tI.SakaiJuchi, and Y.Itoh, Te t rahedron x., 1986, 27, 1599; J.C.Podesta, A.il.Chopa, and L.C.KoL1, 1. &. @. (21, 1925, 308; R.A.Howie, E.S.Paterson, J.L.Wardel1, and J.ll.OurLey, A. Organomet. B., 1986, 304, 301; K.Swani, a.Nebout, D.Farati, R.Kris!indtnurti, and H.G.Kuivi la, Organornetal l ics, 1936, 5, 2370. D.J.Ager, J. B. =., P e r k i n Trans. I, 1936, 133 and 195; E.Schaumann, C.Freise, and C.Spanka, Synthesis, 1956, lL'35; D.J.Ager and R.E?.Edst, J. Org. %., 1396, 51, 3083. n a r b a r o , A .Zat taq l ia , P.Giorqianni , G.Xaccaqndni, D.f?acciantclLi ,

57

53 - . -~ C.F.Bonin;, G.Mazzanti, and P.iani, i. 9. K., P e r k i n Trans. 1; IYXJ, Lj1; 'I.Aonu, C.I.iyodo, Y.Terao, and K.Achiwa, T e t r a h e d r o n u., 1935, 27, 4039; A.Hosoni, Y.~'latsuyana, and H.Sakurai, J. u. E., Chem. Commun., 1933.5, 1973.

59 t<.Hiroi, H.Sdt0, arid K.Kotsuj i , Chern. Lct t . , 19S5, 743; F1.tiannaby arid

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51

62

43

64 65

63

69

70

71

72

73

7 4

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75 70

77

78 79

3iJ

81

22

GJ EI

:: 5

'I I d 0

i j 7

*.o 1>1:

' 3

$I 'I

31

92

3 5

9A

95

36

D.M.Demko, T.A.Jessen, and J .P. Drmers, Te t rahedron K., 1986, 27, 2099. E.-i.rJegishi and T.Takahashi, J. h e r . Chein. z., 1985, 108, 3432. r:.Kusakabe and F.Sato, J. pe~. K., Chen. Commun., 1986, 939 and -. w., 1956, 1475; J.P.FouLon, rl.0ourgain-Comner;on, and J.F.Normant, Tetrahedron, 1986, 42, 1359 and 1399. S.flartin, K.Sauvetre, and J.F.l!ormant, Te t rahedron E., 1366, 27, 1027 and J. Orgdnomet . Chem., 1936, 303, 317; 3.9outevi n, Y .P i r t rdsanta, and L.Sdrrdf, J. F l u o r i n e Chem., 1720, 31, 42s; W.Doenigk, Ii.Dickopp, and D.Wendisch7 P h o s p h o r u s m p h u r , 1930, 26, 253. T.H.Chan and K.KoumagLo, Te t rahedron E., 19d6, 27, 363. L.E.Overman, A.Castaneda, and T.A.Dlurwnkopf, J. h e r . m. =., 1986, 108, 1303; I l . i l iemstra, W.J .Klav?r, and \ : . , u . S p e ~ k a ~ R e c l . t r a v . Chim. Pays-Bas, 1336, 105, 299. Y.Kitano, T.Matsunoto, and F.Sato, J. Cham. S O ~ . , m. Cotmun., 1936, 1323; G.O.FalLon, fI.J.Fitzindurice, W . R x k s x and P.PerLnutter, i\cta Crys ta l logr . , 1935, C42, 1654. K.!.lozaki, K.Uakarnatsu, T.Nonaka, W.TucknanteL, K.Oshirna, ant, K.Otirnoto, Te t rahedron Lett., 1934, 27, 20[17; K.-H.Chu and K.K.Wang, J. a. m., D.J.Ager, il.C.Cook3, II.J.East, S.J.flole, A.Rampersauc?, and V.J.l:cub,

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1980, 51, 757.

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-- J. -

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-- --

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and GI.Ito, J. 9. %., 1930, 51, H36; C.Caulet t i , C.Furlani, F .Grand ine t t i , and i>.F;arton, J. Organornet. C h m . , 19S6, 315, 287. G.P.DoLdrini, E .TayL iav in i , C.Trorhini , and A.Urnani-Ronchi, J. 9. E., Chern. Comrnun., 13F-5, 685; V.J.Jephcote and E.J.Thomas, Te t rahedron G., 1955, 26, 5327. S.L.Larsori, E .Torres, C.E;.Rora tes, and G.J .rlcCarvey, .Organornetat li cs, 1986, 5, 2274; rq.DerZlund, C.Andersson, and R.Larsson, J. 3rganomet. Chem., 1936, 314, 61; Pl.Hoshi, Y.Matsuda, and A.Arase, D ~ J L L . Chen. z. Jpn., 1936, 59, 659. J . I p a k t s c h i and S.Lauturbach, Angeu. Chem. E. Ed. w., 1936, 25, 354; S.E.Uennark, K.L.Habermas, G.A.tlite, and T.K.Jones, Tetrahedron, I%o# 42, 3321, P.Sii Lson, S. 'kolff , and X.C.Agosta, Tetrahec!ron E., 1?Z5, 26, 5533; li.Uno, L u l l . Cher.1. z. Jpn., 1326, 59, 2471.

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lijl Y.II:eda and H.Yar;idwto, OuLL. Chcin. z. Jpn., 19,%, 59, 657; K.K.Wong, S .S.Nakaw, and M.f'l.ilarcano, Te t rahedron H., 1X6, 27, 1'123; P.J.Garrett and A.Tsot in is, m, 2761; i3.R.Trost anci S.Y'iCnoni, - - - J. i)rS. Chiw., 19S6,

97 -

93

- 99

130 G.Young and V.Sitchirig, &&. J. m., 1935, 38, 1767; W.Kitching,

51, 3435. 102 i,'.Franck-lieurnarln, i i .SzUrati, and !'i.fiokhi, Te t rahedron E., IS'fi.5, 27,

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and J.F.tlortiiartt, c, 19CG, 27, 5727, 1339, arid 1043. 1:34 il.Ta&ei "rid A.ihnn, T r t r a h c d r o t l E., 1986, 27, 2313; Y.;;arutd,

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106 P.C.3uLnan PaSe and S .RosenthaL,-rahpJrun Lett., 1936, 27, 1?47 an6 5421; A.Arcadi, S.Cacchi, and F.F:arineLli, z, ;')397; Y.Kita, S.Akai, I J . A j irnura, Fl.Yoshiga, T.Tsugoshi, t.I.Yasuda, and Y.Tanura, J. a. c e z . , 1936, 51, 41%).

107 I i .rhiragami, T.Xdwanoto, K.Ut irnoto, atid H.i,:ozdki, Tet rahedron L e t t ., ICf':, 27, 589; T.Ohnuma, il.iidta, H.i.liydchi, T.Uakamatsu, an:! Y.Gan, -, 217; J.Roser and L:.iberl)ach, Synth. Conrnun., 1YC6, 16, '123; ;1.J .Sc! i ix i t t and C.D.:&dford, Synthes is , l X 6 , 132.

J.J.Eisch, k.J.Pictrous%i, S.K.iiroMiist,:in, E.J.GaSe, arid i.L.Lee, 1. K. -- C i i m . SOC., 1935, 107, 7213; X.i'lach, F.Turccek, il.?%ntro,Jiusovrj, a rx i V.;ianus, d rganorneta l l i cs , 'lYJs, 5, 1215.

ILN J. l?.Fr i tch and P.C.VolLhsrlt, K c . J. m., 1?'.!5, 26, 131 (Che;a. e., 19:56, 105, 172562); H.Butonsclion, K.Wi nk lc r , and X.P.C.Vollhar~.!t, J. m. Sot., Chm. Cummun., 1935, 383; 3,Eaton, J .M.O'Connor, and ~;.P.C.iJoLlharc:t, O r g a n o n e t a l l i c s , 1986, 5, 394; R.Diercks anci K.P.C.Vol lh~r i l t , 11. h e r . Chela. =., 1325, 108, 3159.

::.iii r thsni i icr and i<.P.C.VoLLhari't, J. Ariier. Chen. K., 1(3:;5, 138, 2431;

I i Z V.Eautcnstraucli, U.Surgrr, an? P.iii r t ! insr, Chinia, 1925, 39, 2 2 5 ;

-

113 I:.!kstdagh and K.P.C.Vollhardt, J. m. s., C ! i m . Ccrmcun., 195, 2Gl;

O.Eaton, J.it.Xing,Jr., and ::.P.C.VolLiidrCt, i?rjd, * 7 r - 1-124.

111 I:.Xerstiny, K. i~chnicke, and D.F?iiskc,. J. Oryanonct. Chen., 1936, 309, 125; G , Arnda 1 E li assen, E .KLostcr-Jensen, s n c C.Eor,ini ncj, Acta Chesi. Scad., - Ser.i, ~$XJ, 413, 574; ti.l:atsunoto, K.Akaiwa, Y.ilal;ai, K.Ohrio, K.Inai, S.:?asui;a, and Y.llaracr'a, O r g a n o n c t n l l i c s , I E 6 , 5, 1526.

11? J .Porriet, D.Dainour, and L . l i i g in iac , - ~ Tetrahedron, 1936, 42, 2017; J .Pcrnct, A.Rayadh, and L.Kiginiac, Te t rahodror i %., 1986, 27, 547'1; i;.Hiet,)stra, h'.J.Klaber, and L.I.II.Sf~ecka~np, - i t i d , 1411 ; Y.l<o!iaysshi, Y .K i tdiii),

T.i?atsunoto, and F.Sdto, E, 4775; A.J.i:i,ye, G.Patteriuct,, and S.I,:.Roixrts, isiJ, 2335; 3.5chinzr:r, J . S t e f f t n , and S.Solyuta, 1. -. Sot., ihesi. Cormun., 17Z6, ::3.

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11.:

115

110

117

C .T.;jo?;oradovskii, and V.S.ZavyoroJni i, iLicj, 1,.:25, 129, 17. I;.V.Gir~asuva, E .T.i.X~yorsdovski, 1736, 55, 2135 (CIICIJ. E., 7S.26, 105, L X L ! ' ) , G.Hi iwert and X.cjiesa, L ieS ic ,s A n n . w., 1986, 3 2 ; C.k.RussrL1 and P.iicjirvibdatcRai, Te t rdhodron - Lett., IVdh, 27, 347!?; Y.Yammoto, S .d is i i i i , ancl i(.r';aruydnia, L. m. %., Chem. Comniun., 1986, 102. 3.Mrackneyer, J. a. =., Chrm. Comiaun., 1985, 397; S.Kursch1 anc! Z.Wrackneyer, c, 403 an(i 1. ; laturforsch., T ? i L 3, I?%, 41, 693; A.SebaLd anr! R.\.<:rackmeycr, J. OrCiailornet. Chrm.,F$, 307, 157; A.SebaLd, P.SeiLerLich, arid B.Wriickmeycr, ibiJ, 303, 73. Z.Dje~~haba, i.j.Jousse;rum, fj.i<dt.ier, an6 J .-G.Oui>oudiri, J. Oryanuiiiet. - Chei:~., 19X1, 304, 115; E.G.lluloncy, J .T.Pinliey, and t.ii.itoche, T?traheGror i E., 1?3:), 27, SUZ5. W.S.Trahariwvsky and J.P,scias, J. h e r . m. Soc., 1926, 108, 6829; C.aartoLi, P;.Bosco, 2.SaLl;ozzo~ a n d . t . T o d e s T J. Ory. Cilegl., 1984, 51, 3634.

V.S.Zsvyoradnii, 2. Obshch. Khiiii.,

- --

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112 I.I.Schuster, i i .Weissuristeiner, and <. i i is luu, J. A m r . Chein. E., l9i3C, 108, 6661; iJ.i-:eissenst-iner, l . l .Schuster, J.F.dLoutit, dnii i:.i-jisLou, 9, 6664.

117 ;?.Galas, E. 5. g. c., Ser.2, 1935, M1, 1235' (%. %., 1996, 105, 79021); J.-i.YoshiJa, ;<.:.iurclki, funah ah as hi, d i d ;J,Kauabata, J. O r r j . - Chem., 1C;b, 51, 3996; S.R.Uison and i . k . J c l c o i ~ , J. a. a., 1936, 51, 4333.

722 \!.iiauboLG, J.HardtLe, \J.GoLLinycr, anc iJ.Einiiolr, J . dryanonlet. Che;,i., 1%L, 315, I ; Il.A.Crune, R.iless, and G.Schniidtberg, =, 303, 429, id.Umura, T.i;;oi.!rrydshi, T . l l i n m i , and Y.li;yashi, Te t rahedron w., 1336, 27, 2479.

121 il.E.Katz, SrGsnomctaLLics, I??$, 5, 2.53:: and J. A n i r r . Chei~. sc)c., 1726, 108, 7443.

122 J.-P.Drsvergne, ii.Borias-Laurent, A.CasteLLaii, J.KowaLski, E .Yurek, and A.utl t iaut ;k Sigy, J. Cliern. SOC., 3. Commun., 1?G5, 82; ti.Sakurai,

. i 'hosphorus Sulphur, 19?:h, 27, 205; J.Fu, !iuaxuc3 S h i j i , 1325, 7, 322 AL?., 1935, 105, 134915) .

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l:.Kitching, H.A.3Lszowy, I .Schot i , LJ.Rdcock, and 3.P.Cox, J. Drganonet. Chern., 1926, 310, 269.

125 =enssen and A.R.Aartin, Heterocyc les , 1?55, 23, 357; M.P.idwards, A.I!.Doherty, S .V.Ley, and H.M.Orrjan, Tetrahedron, 1906, 42, 3723; S.Shirnizu and !4.0gata, J. a. m., I?%, 51, 3?97; P.Uernbech, G.Seconi, C.Eaborn, J.A.Rodriguez, and J.G.Stampcr, J. m. E., P c r k i n Trans. L, 1796, 197.

126 rl.'r!.llajchrzak and G.Simchen, Tetrahedron, 1956, 42, 129?; A.Dondoni, A .8 .Kast e L La r i , A.r'?cdi c i , E . !:eyri n i , and P. Pcd r i n i , S y n t h e s i s, 1986, 757; S.S.IJikam, K.-Ii.Chu, and K.#.Wang, J. Org. Chem., 1956, 51, 745; D.J.PolLart and B.Rickborn, -, 3755.

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gryanonet. Chem., 1926, 316, C4; M.J .Henderson, R.I.Papaseryio, C.L.Raston, R.H.IJhit?, and A.F.Lappert, J. %. z., Chen. Cornmun., 1986, 672; S.I.BaiLey, O.CoLyan, L.K.EngeLhardt, W.P.Leuriy, Z.I.Papaseryio, C.L.Raston, and A.H.White, J. m. g., D a l t o n Trans., 1936, 693.

- Amer. *. =., 1936, 108, 4222; Y.Yaiaarnoto, Y.Gzuma, and H.Mitoh, Synthesis, 1356, 564.

- Chcn., 1986, 316, 249; S.Tomoda, Y.Matsunoto, Y.Takeuchi, and Y.Nomura, -- Chen. L e t t ., 1985, 1193; P.Cro t t i , F.flacchia, A.Pizzabiocca, G.Renzi, an6 M.Speranza, J . Chem. z., Chem. Commun., 1906, 435; Y.Takeda, T.Matsunoto,-anzSato, J. 9. *., 1986, 51, 4722.

-

- ~ -

-- (w. 123 S.S.lql-DiaL, J. m. s., (21, 19ZG, 3'56; C.BreLiere, F.Carre,

124 R.iJeidlein, h'.Eraner, and !I.Uirth, HeLv. Chin. Acta, 1935, 69, 1597;

--

128 F.llaassarani, M.Pfeffer, A.L.Spek, A.M.I!.Schreurs, and G.van Koten, J. 129 E .Lukevics, V.V.Di rnens, Yu.Sh.Goldberg, and E .E .L iepinsh, J. Organornet.

126

130

131

132

133

134

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'1 37

154

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1 /*I


@.K.Dent, i;.lizlton, arid A.N.F.Smith, m. J. 3.. 1985, 39, 1L21; F.iiruger anti G.Szl;iinies, TetrahcrJron E., l%b, 27, 1563. K.A.Kirms, ll.Primke, ::.Stohlnieier, and A.cje I t e i j e r e , ;?ecL. Trav. Chim. Pays-Oas, 1?1;6, 105, 462; 14.s .Kai r d anti H.ii.tiussai n, T e t raheuror i E., 1926, 27, 5143; R . i k i d L ? i n and D.Christen, t l c l v . Chim. Acta, 1186, 69, 1523. E.R.Davidson and V.J.Shincr,Jr., J. Amer. Ctieni. *., 1936, 108, 3135; L.A.Paquet tc, t.l.iloppe, L. J. Johnson, K.g. InyoLd, T e t ra i iedron E., 15'36, 27, 411. i i .Grignon-Dubois anci J .3uriogues, J. Urganomttt. Chelii., 1326, 309, 35; i!.T.ConLin and Y.-W.#wak, 3 r p n o r n e t a l l i c s , 1936, 5, 1235; E.Nakdrliura and I.Kuwajirna, T e t r a h e d r o n E., 1936, 27, Z3. A.l<unye arid IJ.SanJer, Tc t rahcr i ron x., 1326, 27, 5835; G.L.Larson, V.Cruz de IiaLr!onado, and K.R.L:errios, Synth. Commun., 1956, 16, 1347. T . i i i r w , D.[iisu, and T.Agawd, J. m. z., Chcm. Commuri., 1Y26, 2 6 ; Y.ilJtanska and I.Kauajima, T e t r a h e d r o n e., I??&, 27, 719. L .C i rko fer and D.Eichstadt, i. Organoinet. Chem., IT%, 307, 279; K.Dakltouri, J. c. Struct . , 1935, 130, 209. 3.L.Chenacrc:, Te t rahedron E., 7'186, 27, 2:?U5; i).iJ.Chernysheva, T.K.Gar, A.'J.Xisin, and V.F.f:i rilnov, ;:.Lak%ouri, - - Zh. Obshch. Y\him., 1135, 55, 2333 (Chem. Abs., 1936, 105, 209962). I<.Janss?n, T.Frejd, J . K i h l k r g , and G.cagnusson, Te t rahedron E., 1'?:;5, 27, 753; S .-;{.An and i,'r.:obek, i d i d , 3219; R.i:unstedt and U.Wannagat, Plonatsh. Chcrn., 1385, 116, 6?3. L.E.GuscL'niZov, Yu.P.Folyskov, E .A.Volnina, V.G.Zai kin, and lJ.S.ilasietkin, DokL. Akatl. tauk SSSR, 1C85, 282, 901 (e. e., 1965, 105, 42702) ; rJ.v.iJshakov, E.~.Cshinci, and 'J.R.Vdovin, I z v . E. -- I-!auk SSSR, Sfr. %., 1955, 13136 (*. +., 1936, lQ5, 790'36!3r iJ.Aunt?r, I.l,:i.T.Gavitlson, S . 1 jatl i- l laghsr;odi, and F.T.Lawrence, Organometa 1 t i c s , 13Z6, 5, 431; V.i'i.Vc:ovin, N.O.Bespa lova, and t:.O.Sergeeva, x. Akad. kauk SSSR, z. -., 1735, 1917 (Chela. E., 19S6, 105, 60673); K.E.Colvin anc: ;i.F.Schaefer,III, Farac'ay Synip. Chen. - Sac., 191!4, 19, 3:) (m. &., 1 X 6 , 104, 143922). M.Ishikawa, H.Sugisawa, Ii.Akitorno, K.Matsusaki, S.Kamitor i , K.Hirotsu, and T.Higuchi, Crganornetal l ics, 1986, 5, 2447; f l .Ishikawa, H.Suyisaua, S.Matsusawa. K.t l i rotsu. arid T.Hic:uctii. i b i d . 182.

-

--

-- --

142 Il.Ishikawa, J.Ohshita, Y.ltc, O r g a n o n e t m c s , I ~ C ~ J , 5, 151.Z; E.Isliikawa,

143 G.r i .sRi i t t i , J.D.Caryenter, arid T.J.ihrks, 1. Arner. Chern. =., 1926, 108, J.Ohshita, Y.Ito, and J.Iyoda, J. Amer. Chem. K., 1'286, 108, 7417.

6805; i3.J.J.van da i l e is ieed, J.J.Cartholoneus, G.Schat, O.S.Akkerman, and F.3icki?lhaupt, Organornt?taLLics, 1936, 5, 1749; L.Andreucci, P.Giversi, G. Ingrosso, A.Leucheri ni, F .Rarchet t i , V. Andovasi a, and r?. ?;a r t k l ti, J. Chm. Soc., D a l t o n Trans., 1?35, 477; H.SLizLiki, T.Tsukui, and Y.b?oro-Oka, - - J. Drganomet. w., '1926, 299, C35; R.H.ChishoLm, J.A.Heppert, J.C.tluffman, ant! iJ.E.Straib, J. z. s., Chen. Commun., 1985, 1771.

144 M.Fajardo, K.P.Gomez-Sa1, P.Royo, S . i r iar t inez Carrera, and S.Garcia BLanco, J. Organonct. Chem., 1986, 312, C4lr; C.3Lom, J .;3oersma, P.11.1S.31~dzeLaar,. t l .Fischer, A.Haaland, H.V.VoLden, and J.Wedlein, Acta Chern. Scand., Ser.A, 1936, 40, 113; P.C.ULake, H.F.Lappert, J.L.Atwood, and H.Zhang, J. z. SOC., Chem. Commun., 1336, 1148.

1926, 315, 143; I.K.Outler, W.R.Cullzn, and S.J.Retti9, Oryanometal l ics, 1386, 5, 1320.

F.Ludenann, and H.Kopf, J. Organornet. Cliem., 1986, 303, 167; R.Daumann an6 U.t.":aLiscli, E, 303, C33; J.Hcck, E, 311, C5; W.AbrieL and J.tieck, - i b i d , 302, 363; il.f.Wright, G.J.Lon6, D.E.Tharp, and G.O.HeLson, Oryanomctal li cs, 1926, 5 , 770.

Enyl., 1935, 25, 738.

-- --

---

145 m . D o o t h , G.C.Offune, C.Stacey, and P.J.T.Tait, J. O r g a n o w t . Chela.,

145 P.Jutzi and R.Dickbreder, m. %., 1986, 119, 1758; J.t:uLler,

147 :J.Hock, I.l.Oroschin, C.Paolucci, and R.D.Fischer, Anyew. Cheni. x. Ed.

148 P.Jutzi, D.Kaime, and C.Kruyer, Angew. Chem. x. Ed. w., 1986, 25,


164 .

Organonet. *., 17%5, 299, 2::s; P.Jutzi, L?.Ha~pct , f'i.r:.l!ursttiouse, a110 A.J .:lowes, L l r ~ e n d r n c t a t l i c s , 1925, 5 , 1944; P.Ju tz i and i.l,lianp?L, - i s i d ,

143 P.Jutzi, E .I;cliLuter, K.O.tiursthouse, A.K.Arif, and R.i.Short, - J.

730. 15!> P.Jl;tt i 2nd 2.ilampeL, J. -- Organonrt . w., I?%'), 301, 2;:3; F.X.KoliL,

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1 5 2 il . L . W i L L i am s o w J rgario:,ie t L L i cs, 19C6 ,. 5, 21 4 2; !I .S chu~:ianti,

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---

-

Chehi., 192.5, 307, 7. - 157 J .i)ubac, A.Port:?ri c, ;.f'aiiueL, a n d '1. I L O U ~ h i ? ~ J ; ; ? , ?+osp! iorus Sulpi iur , 1926,

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159 S .E .Crc?iner and C.ZLanCenship, OrgariorilctdLLics, 14:%, 5, 1329; il.AppLer and !:.P.F;eurnanri, - J. grganom;.t. u., 1926, 314, 247.

155 ~:.T.Nguyen ail(:' F.K.Cartledg~a, J. a. Chcl;l., 19S6, 51, 2213~5; T.Dutkouskyj W a t k i w and G.Szeimics, Tetrahedron, 10S6, 42, 1245.

161 Y.r!akaJaira, T.Kobayashi, and Ii.Sakurai, E. w. z. JFrl., 1?f'5, 59, 1507; C.-li.Lin, C.-Y.Lee, and C.-S.iiu, J. h e r . Cher:i. sc)c., 1926, 103, 1323.

1.52 f?.ir;lckmeyer, J. Organornet. Chem., 1386, 310, 151; S.KerschL and 3.Urdckrneyer, J. m. K., Chcm. Comnun., 1936, 1173.

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154

165

166

167

168

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17i,

171

17:

175

174

175

17\!

177

173

173

1 :;:!

1 :;I 132

13:

1 ':5

1 (:b

1 S7

It13

1 ; d l ???I).

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108, 424.1.

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-- ' T.A.BLinka and R.West, OryanomctaLLics, 1326, 5, 123 and 133;

, E .tlenijg:?, U . K a l c h a u e r , Y d F.Schronk, Honatsh. Chern., 1986, 117, 1399;

129 Group ZV: The Silicon Group

183 J.R.Damtwood,Jr. and R.Camboyi, Tetrahedron, 1956, 42, 6411; F.Shafiee,

1YO K.Takeda, tI.Teranae, and rJ.Ratsumoto, J. Anrr. Chcn. %., 1986, 108,

191 L . t < i t t e i l u n g and i;.tidssLer, t4onatsli. Chein., 1366, 117, 613; il.ll.Chen and

192 A.tq.Arif, A.H.Cowley, T.r<.ELkins, and d.A.Junes, J. m. z., m.

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J. i l i rndt , J. Organornet. Chem., IY?], 301, C21; S.P.Lolesnikov, X.P.Egcrov, A.d.GaLmiras, A.Krebs, and O.M.iJefeoov, I z v . Akad. IJauk SSSR, Ser. #him., 19S5, X 3 2 (9. &., 1936, 105, 17ZJll). - -- - -

196 ;I.?uff, t I . i k i s ig , k'.Schuh, and b.SchdsL, J. Grc,'inomet. Ciiein., 1925, 303, 343.

193 G.Ihrk1, (I.Horn, and W.SchLosser, T e t r a h e d r o n E., 1Y:15, 27, 4919;

134 c . S m n d A.Schrnke1, T r a n s i t i o n P:eti;L Chcm., 1985, 10, 210;

195 G . d e f e d o v , il.P.ELdrGv, A.f.balminas, S.P.Kolt?sriikuv, A.Krebs, ano

201

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313 Lz.L.Chcrnar3 and C.M.van Zyl, J. 5. e., 1994, 51, 35fJ:; S.L.Cherridrd, 145.

C.::.van ZyL, and O.R.Sanderson, T c t r a h e d r o n s., 1936, 27, 28:Il; Y.Ito, T.iknilo, T.l latsuura, and iF.Ishikawa, J. m. z., Chc-rn. Conmun., 1336, 98U.

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255 i;.L.Mandict,, W.D.i:aents,Jr., find V.L .3onriyb,cy, 1. Phys. Chcin., lC3.5, 90, 2315; A.l'.Doticaster and R.UaLsh, J. m. g., Fdraday Trans . z, 1756, d2; D.J.Hajdasz anc ;i.P.Srjuires, J. A w r . Chem. SOC., 1%36, 108, 3139.

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206 A.GekLat, L. Ch;?n., l?65, 25, ? 5 9 (m. z., Im, 105, 65.59); .,ckers, ti.rjurc;i?r, E.Eujen, B.Cenpfer, c;nd il.3bc-rliarnmc?r, J. s.

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210 L . B i r k o f c r and K.Grsfen, J. Organornet. Chen., 1956, 299, 143; X.Tanao, T.Tanaka, T.Phkafima, R.Sumiya, I+.Arai, and Y.Ito, T e t r a h e d r o n E., 1986, 27, 3377.

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, 314, 75: D.:l.lladdlvton, -, 311, C21. 217 :7.8rocbirianri, i i .toin Dizck, and I. l<Li.inirLichter, J. Urganuc i r t . Chen., 1936,

211 S.Anwar and A.P.Davis, J. m. =., m. Cornrnun., 1936, 831; G.A.Olah,

212 H.Ssno, Il.Ogata, and T.Misi ta, Chern. Le t t . , 1986, 77; G.A.OLah, T.Yamato,

213 M.Fujita, H . i l i sh i , and T.Hiyana, Cheri. L e t t . , 19S6, 837; H.8rurincr,

214 C.Aitken, J.F.tisrrod, and E.SarnueL, Can. J. w., 1986, 64, 1677; f.l.Xnorr

-- 215 A.Sisak, F.Ungvary, anc; L.Rarko, O r g s n o x t a l l i c s , 13St, 5, 1313;

- - 216 Il.i:.~iakoLs-Christi3noC.oulou, J. OrGar,unct. Chcri;., 19.16, 308, CL4;

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309, 345; 3 . S o u t i v i n , Y . P i e t r a s a n t a , and J.Youssef, J. F l u o r i n e Chej . , lt2eb, 31, 57.

218 L.;:.Lewis and l i . iewis, J. Amer. C l l r i r ~ . Scoc., I?", 103, 7222; K. J . Fe rnarrdez, X. A .E s t e r u e h s , Y.S . J i r n i r e % , arid L . A . O m , 0 r g a n m e t a L L i c s, 1Y.5, 5, 1513; ; l .SchubFrt snc! J .Burijeri,. -~ J. Organornet. -., I?%, 3a3, C5; :<.::.::egman, OrCanone taL l i cs , 14M, 5 , 7!:7.

219 S.I:ohda-Sudoh, S .Ka t r3g i r i , S.I.Kut6, and S.!ibwra, J. f io l . S t r u c t . , 1335, 138, 113; H.Shrifi, Y.:liyszaki, :l.Ol;arrars, anr! Y.Ucno, Synthesi;, IBCC, 77C; R.Eujr?n, ?.i+lLies, ant; k .?c t rauskss , L. Or?janoriir?t. Chen., 13.36, 299, 29.

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2 2 % i.i.Tanaka, t i .Myt ika lda, ;;.3b.i, T.i.iyds"k.~, Te t rahedron , 132.6, 42, GIS7; S.A.Jul ia an6 K.Lariw, -- ; L i t , 5?11; :;.Deyu?i L-Castainy, A.Rshm, and :i.Dci!iitn, .- J. - C r g . - Cheni., lvcf,.. 51, lL.72; ::.ano, I . ! l aon i~c ta , anti ; \ . i h j i , - J. - Org. CJEJ., 1926, 51, 21?32.

223 L).il.i:.Uartun, b.Cr ich, an.: : i.f iretzsc!iciar, J. Chern. SOC., P e r k i n T rans . I-,

C . A. To L s t i kov, 9: .S . l't i j t nkov, ;1. A. 3i t ? i 1 ova, Y 5 . L . Ve 1 ' de r, 5 y !I t l ie 5 i s , 1926, 4%; V.P.Z:si LarG.?on anti J.K.Sti l l c , J. h e r . Chcil:. x., 1SB6, 108, 452.

T.Araki, T.EriCo, and fi.l)kawara, c, 215; P.Kocovsky, l .S ta ry , and F.Turcc?!k, *, 1513;E .IlsgnoL i r id Z . I m k L d c r i ~ , -, 2 2 5 5 ; >.P.Curran, K.-:l.Ctien, arid O.Kim, J. - A m r r . %. si)c., 1926, 108, 24%.

2 2 5 Y .Sa%aguchi and il. l layashi, Phys. %., 1X5, 90, 55::; D.1-l.I:.Uarton, 3 . C r i ch, A.Lobberding, and T E Z a r J , Te t rahedron , 1936, 42, 2529; J.A.Franz, rl.K.Suleman, and : ' .S.Al i ia j jar , J .fl.HanckeL, S.-l:.Lee, D.Zus!iinan, ~ n c ! T.L.i'rown, I n o r g . Chem., 1?1;6, 25, 1252.

220 L.Ft;bry, P .Po tz inse r , ~:.it::irii~n~i, A.f?i ttttr, ancl t i .P.Steciibergfn, Uryanor,:et.illics, 1!2tZJ, 5, 1231; T.J.Gartun, A.i:?vis, I.fi.T.Zavidson, S .Ijadi-l.!dyhsocJdi, i<.J .k1ughes, and f:.S . tordon, J. A w r . Cheiit. .- Sac., 1325, 108, 4022; :i.Auner, i?.MaLsh, and J .!Jestrurp, J. GCh. %., C!icm. Cominun., l?35, 2117.

- - -

220 T.3 i r cha I -1 d n 6 V.lldnivannan, J. E. z., 3 a L t c n Trllns., 19;;5, 2671;

221 F.Guibc, 0.3anglcs, and S.PaLavuir\e, T o t r a h e d r o n L e t t ., I%&, 27, '1365;

- - - -- 1 7 ~ ~ ,?c, 39; i).i:.,lones and fi.i:.Peel, I. Chea. Soc., Ctiern. Cornnun., 1%?6, 215; --

22:; Z.J. \ l i tcz i lk , T e t r a h e d r o n LF t t . , l?r6, 27, 155; Y.C:ananabe, Y.uerio,

- - - J. O r c : . Chm., 1936, 51, 19;


227 R.A.Jackson and A.K.Zarkaois, J. Chem. Sac., Chem. Coralnun., 19136, 205; ti.Stork and Vl.J.Sofia, J. Amer: Chem. g, 19Y6, 108, 6326; M.T.Craw, A.ALberti, M.C.Depew and J.K.S.Wan, O u l l . Chen. z. Jpn., 1386, 52, 3675; A.Albert i , C.Chatgi L i a l o g l u , G.F.Pedulli, and P.Zanirato, J. Amer. Chem. - Soc., 1930, 108, 4993; J.P.Sarasa, J.IyudL, and J.M.Poblet, J. 3. K., P e r k i n Trans. 2, 1936, 361.

228 M . i < i r a , G k a T a w a , and tt.Sakurai, Chon. Lett., 19S5, 497 and 1935, IS41 and 1245.

229 C.GLiJeuclL, J. Oryanomet. Chen., 17i?Lt 303, 337; M.Kobayashi and b?.Kobayashi, B u l l . Chem. z. JFn., 1936, 59, 2807; N.Kobayashi, ll.Yoshida, and F:.Kobayashi, -, 3169.

230 K.rlochida, M.Wdkasa, Y.Sakaguchi, arid H.liayashi, Chem. L e t t ., 190i5, 1793; P.t1.& ;':yck, S.Hoste, and G.P.van d e r Kelen, c. *. Chiin. Eelq., ?'?:36, 95, 217; J.Lusztyk, D.XaiLLdrd, and K.U.Inqold, J. Ory. Cher;l., 1986, 51, 2457; li.P.IJeumann and R.StapeL, -. s., 1395, 119, 3 4 3 2 .

231 E.OunceL, T.K.Venkatachalam, 2nd J.EdLund, Can. J. a., 1 9 X , 64, 1674; :;.I.\ochiaa, S .Okui, K . Isfi ikawa, O.Kanakuho, T.Tsuchiya, and K.Yanamoto, - Chcm. e., 1385, 3i35; Y.Ito, T.I:atsuura, S.:Jishilaurd, an3 :l.Ishikaua, Te t rahedron w., 1986, 27, 3261; J.C.Shelc:on, J.H.DGui?, C.H.Du Puy, and R.Darnrauer, J. A r w r . Chew. %., 1986, 108, 575%.

I .F leming and A.P.Thonas, w, lr,56; A,Alexkis, J.DerLan, and Y.'Jesace, Te t rahedron w., 1936, 27, 1847.

233 L.Rosch, J.Pickardt , S.Imme, and iJ.Dorner, I. i h t u r f o r s c h . , T c i 1 G, 13.36, 41, 1523; W.Tuckmante1, K.Oshiriia, and ii.iiozaki, *. x., 17:36, 119, 1 5 8 1 ; i: . i j a k am 2 t su , T . ?io na I< a, Y . i) k u d a, L: . T u c k lil a n t P I, K . 0 s h i rn a, K . U t i mot 0, and il.:!ozaki, Te t rahedron , 133i, 42, 4427.

2161; K.iiaast:, U.KLingebie1, R.Ooi:.se, LYIX K.fJclk, w. K., 13%G, 119, 1117.

A.b.Avent, C.t:jborn, :?.P:.A.Z 1-KlieLi, FI.E.MoLLa, J.D.Smi th, arid k.C.SulLivdn, J. Amer. Chen. E., 1985, 108, 3Z55.

-- Chem. Lett., 1935, 513; K.f!ochidj, M . W a k ~ s d , Y.Sakagichi, and il.Hayashi, i b i d , 773; f,.i(iyooks and A.::iy;uclii, i'Jiif, 1.Z23.

104, 149323 1 ; 3 . A .i! ravo-Zhi vo tob sk i i , S . D .Pi 94 rcb, 3. A. Vyazsnk i n3, and ::.S.Vyazankin, 2. 3bshch. Khirn., 1725, 55, 2396 (m. &., 19015, 105, 1 S 3 1 611 1 ; 0. A . 0 ravo- Z h i vo t i)v s k i i , 1 .S . S i L t u Eva, 0 . A . V y a za nk i ns , a nti N.S.Vyazankhin, z. Akad. tjauk SSSI!, 2 ~ . -., 19G5, 1214 (-. &.,

232 1.FLening and F.J.Pulido, J. -. E., Chela. Coonun., 1936, 1U13;

234 i:.FQrJarni, K.Os%ims, E.Utirouto, and t i .Xotaki , Tet rahedron Lett-., 1936, 27,

235 A.SetjaLii and L%.Wrackineycr, Sp;tctrochim. Acta, P a r t A, 19?h, 42, 1107;

236 K.t.lochida, M.Uakasa, i-i.?:urai, Y.J. I ' l iaya, Y.Sskaguchi, arid H.i-layashi,

237 K.!lochida and T.#ugita, t i ipycjn Kagaku K a i s h i , 1985, 334 (m. A&., 1'7'36,

1926, 104, 33712). 233 \i.T.3ychl:ov, V.V.Sharutin, S.P.i?oLotobA, t1.E . i r r lwsi tk in, an6 T.ll.Koiikina,

23') 2 5 11

132 Organometallic Chemirtry

245

247

P.O.Dentz, J.Ruiz, O.E.Llann, C.:?.Spericer, and P.M.llait l is, =, 1374; J .S . X i c c i , J r . , T . F. Koe t z Le, K. J . Fe rnancirz, P. 1':. f4a i t L i s, and J . C. G reen, J. dryanornet. Chem., 1986, 299, 333. D.Perugini, G.Innortd, S.Torroni, and A-Fof fan i , J. dryanornet. ChPin., 1356, 308, 157; T.rl.Arkhi rerva, d.l<.3uLychev, A.M.Protsky, G.L.Solovi.ichi k, and V.K.ScL'sky, -, 317, 5:; A.lJ.Protsky, i;.f.i.9ulychcv, G.L.Solovei chik, atid V.K.EeLsky, I n o r y . C h i i n . Acta, 1936, 115, 121; C.C.Otiyiriuka, S.J.Rettig, und A.Storr, Can. J. -., 19%:, 64, 321. F.W.3.Einstcin, E.#.Porneroy, arid k.C.Ui LLis, J . Oryanoniet. Chzrn., I?%, 311, 257; X.Wany, X.Zhou, J .Zhany, Y.Xia, R.LTu,-tig>xue .- longlac, 1335, 30, 1515 (w. A&., 1326, 105, 2i13C07); :.:.Porchia, U.CdseLLato, F.Ossola, S.Rossetto, P.ZaneLla, dnd E.Graziani, J. E. SOC., Chcm. Cc;rnmun., ??1X, lC34. J.&irLuenga, J.Joylar, S.Fusteru, and i'.Civtor, J. GtE. z., e. Coinmun., 1926, 361; H.Eeckers, ii.::urcer, P.i3ursch, and I.itupyc.rt, 1. i r r y a n o w t . Chem., l?X, 316, 41. L.E.Overrnan, It.E.Okc;z;ki, ax ! P . . I !-'i..!. a.ird, T2 t rahedron L,,tt., 1335, 27, 4391 ; A.A.GaLnn, T.'J.Lee, and C.S.Chapl?o, E, $?95; i2.-L.Conip.3gnon, F.Gilsqucz, and T.Kirniiy, gyn thes is , ~?:YI , 9h?; 3.i.FerinGa a r x ~ J.F.G.A.Janscn, _Tetrahedron E., 1325, 27, 577; i>.P.PtliLLion, R.l!ruSauer, anc! S.S.Andrek;, J. 3. w., 1936, 51, 1613. A.A.Lhdanov, O.A.Astsyov, snci i? .A.Di; l i t r i c i i w a , Zl i . i3l;shcti. h;him., 1925, 55, 7733 (Chen. - A&., 1,33t, 105, 42@0-3), ::.Okdrtu, T.!brumtc, ariL l:.S?l..iyz, Chad. Pharm. Dull., 1975, 33, 222C (*. A&., 1926, 104,. 143967); T.Hvidt, d.i.:.I;artin, Grin3 ;,!.A.Szars2k, T e t r d h c i r o n w., 13c';, 27, 3C07; F.Kdrictdni, E.Oka ia , and t : . : legor@, I3uLL. Chern. z. Jx., 13r.6, 59, 2517.

--

-

--

- --


b! . F .Mciiams rii , E . ; i .7ucs L e r, and F! . T . P? i ne , i) r g s ~ ~ r , i e t a L L i c s , 19%5, 5, 17(+7.

A.U.Bae, and L.F.D.qI.11, -, 5942 ; r ~ . ~ ~ . ~ ~ L i , i s t ~ ~ = ~ r ! , P.?.Por:or, snd rJ.Siyi'L. I n o r y . ChFn., I?.?;,, 25, 1C;Z7.

6414; S.:l.tlawkins, P.D.tlitchcock, !1:F.L.app.:rt, and A.i<.Rai, J. x. z., Chem. Coinmun.. 1??6, 1139; J\.Dorn::,nc., A.AaLiti,. a n d C.I!oise, Ts t rahedro t l L r t t . , 1126, 27, 1477.

%:A 3 . S i i i w and I:.Einz'ian?:, S;fnt:ifisis, I Y 5 , l"45 acci T p t r a h e d r o n Lett., 19Ei5, 27, 4423; S .Tono&, Y.f~~atsurnoto, Y.Takeuchi, ar,J Y .i<dmura, 3 u L m h t : m . S O C . Jgn., l??t, 59, 32?3.

DaLtsrt Trans., l X 6 , 255'; V.P.Kozyu!cov, E .V.:;uzovskaya, and V.F,f,lironcv, - Zh. Qbshch. K l i i i i . , 1385, 55, 11?53 (Chern. As., 13;?b, 104, 62913); Y.Szto, S.:!&fi, K L i r i , i.i.Shirai, and Y . K i i K a Z O E , Tet rahedron w., 1Y85, 26, 5547.

2i56 A.R.!.kssindzLc 2nd T.Stout, J. Chm. g., P e r k i n Trans. 2, 1966, 221; A.R.Dassindalei J.C.-Y.Lau, T.Stout, and P.G.Tayler, E, 227.

237 Y.;lurli and K.r!.Lhine, 3 rganomcta lL ics , 1386, 5 , 2?:;1; !?.!i.Cragg and C.K.:la, J. - Crsanornct. x., lr?:*C, 304, :!7; K.liorchLer, C.Stader, anr; :>.Wrzlckineyer, Inorg. Chira. Acts, 1'736, 117, L3?.

:-'.$utter, and C.D.Weis, 1. Ory. z;., 1916, 51, 55?.

Z.Lasocki and rl.llitekoua, 1. Organmet . m., 1936, 311, 17.

i b i d , 3 X C .

li.Noth, Ii.Prigge, A.-!?.Rotsch, S .Goainathan, en6 J .k'.tJi Lsoii, 1.

R.ii.i:ei lson, I n o r g . Chem., 1 ? 2 ~ 5 , - % 1 ; A.l;eller and I:.Ar~irbrecht, =. K., 1986, 119, 1; T.Frant, C . thnccksr, ii.,Joth, k:.Stocker, id.Storch, and ti.Winter, isiJ, 3CO.

J.E.i3osys, A.14.CowLey, J.G.Lcc, M.PdkULSki, arid J.;l.Poder, J. h e r . Chen.

274 S.K.Vasisht, E':.Soocl, :4.Sooc?, arid G.Sirijh, 1. Orsanonet. Chen., 1906, 301,

275 D.ii.Florton and R.H.Flei lson, Phosphorus Sulphur, 1?35, 25, 215;

262 R.L.Zedat-d and L.F.DahL, J. hist-. Chem. SGC., 1%5, I=, 5033; R.L..3edard, - - - -

253 fi.D.Fryzun, P.R.i:ac!&il, anr' I:.C.r;aLL, J. l,n?r. Cbrein. SOC., IWh, 10.3, - - - - - -

-- 2 5 5 S.Cradock, C.li.:.iuntlEy, !).U.;l.Ei>nkirt, 3ni! !I.Z.Csbertson, J. Chcn. S O ~ . , - - -

- _I____

2Stl :r.3.Weiscnfels' and M.D.Zi LLer, Synth. Cornnun., 19.26, 16, go?; i l .Fr i tz,

26? O.GraaLinann, U.Kl inyebieL, and F.RJtt>ias, 3. K., 1926, 119, 872,:

273 I3.iiLaser and H.lloth, - Ch:?r:i. E., 19SrS, 119, 335;:; P.l<oll? and ti.Moth,

271 R.%ocsc and IJ.Klingebie1, 1. Organonet. Chea., 19Eb, 306, 295; D.!-lannig, -, 310,

-

272 il.iJOth, P.Otro, a m ; i.J.Storch, C!iei,i. Oer., 1?3h, 119, 7517; B.L.Li and

273 ?.KolLe, H.i<ot!i, arb: R.T.Paine, m. x., I??&, 119, 2681; A.X.Arif,

*., 1326, 108, 6033.

15.

U.I.!oLf sbcrger, *.-a., 1986, 110, 650 and 415; H.V.Roesky, U.Seseke, Y.i-;oltmeyer, P.G.Jones, an6 G.%.SheLJrick, A. m. %., D a l t o n Trans., 1926, 1303; U.KLicbisch and U.Kl ingel ieL, J. Organornet. Chem., 1986, 314, 33.

276 A. I:. Chernega, 5. Yu .Ant i p i n, Yu.T .S t ruch kov, 1 .E .Go Ldesku 1, E .O.S Lebanski i , and V.C.Rotnanenko, z. Aka?. ::auk SSSC, K. m., 1925, 2234 (E. - Abs., 1936, 105, 191213); E .iiiecke, M.Lysek, and E.Symalla, Chiniid 1986, 40, 292; O.J.Sclierer, K.Forst inyer, J.Kaub. and W.S.Shr?ldrick, E. e., 1986, 119, 2731; K.lJtvary, I:.Galle, A.Ii.CowLey, and A.R.krif, Flonatsh. - Chem., 1'?86, 117, 1245; R.Cartsch, J.-V.Ueiss, and R.SchmuLzler, 2 . Anorg. ALlg. Chem., 1336, 537, 53; L.!?eiseL and D.Sturln, %, 539, 137;-

- G.Settermann, D.Schonhurg, and R.SchmiJtzter, Phosphorus Sulphur, 19C6, 28, 327.

J. Asrer. u. %., 1356, 108, 7481; W.Veith and V.Huch, J. Drganonet. Chela., 1956, m8, 263.

278 X O a r i i s t e r , Z.V.Hauptnian, J.Passmorr, C.-:l.Uong, and P.S.Uhite, J. Chm. E., D a l t o n Trans., 1956, 2371; ii.-G.Hsuck, I J . W i L l ing , U.Fluller, and- K.Dehnicke, I. Naturforsch., T e i l i3, 1986, 41, 225.

2, 1P35, 41, 799; D.Frst, C.Habben, and A.RalLer, e. x., 1986, 119,

277 11.-G.Schafer, W.U.SchoelLer, J.Piienann, W.tlaurj, T.DaL>isch, and E.Nieckr,

- -

279 C.liabben, A . k l l e r , M.Nolterneyer, drid G.l1.Sht.Lorick, I . tdaturforsch.,


a - 1 7 . 1 . , c . q - c i A ? ~ ~ ' 1 - . driti A.KeLLer, c, c;.

2i;il i;.Dni>k.,c;sl;i, J . i : ichslski , and Z.Skrzypczynski, Phos;hcrus Scr lpbr , l?X, -- 26, 321; T.G.Uack cind R.b.K?rr, Can. J. Chela., 1'?26, 64, 308; F.Fockt!rliJery and A . ! h a s J 2 . 1-Aturforsch.,. Te i ! 3, '11736, 41, 413; i).SchomG?rS, A.Claschettt?, an<; i .lJi?t;jnd,

231 :':.:ivir?r?-Oaudet, G.Lacrampc, J .Zatge, ?.Gervst, snlj ;\.?brchaii\:, Synt;;. EeJct. Inori;. I?etdL-Org. a., 13?A, 16, 991; J.i!.ouriy, J.F.SulL1votl, and Ci.?l.Attia, S l iec t roch in . E, P a r t A , 198b, 42, 75.

2C2 ::.c.r;oLLoy, t<.QueLL, S.J.i.ilunc;cn, ~ n c ' ic.tii L l , J. D. z., DaLtirn Trans., I S X , ~175; K.LcertucrlLo, J.F.bauC;cy, i;.Crjnozzi, ;id ij.i:bsso, Oryanorneta L L i cs, l'??i'l, 5, 1:3hb; C .A .OSsfen i , J . A.Oba Leyc, and 1l.S. Akanni , Synth. Resct. Inorc;. t. letal-i)rr. m., 1954, 16, 777.

2.:3 K.Jurkschat, A.Tzschach, zne. f :? lun i :? rc -P i r c t , J. 0rL;ano:ic.t. -., 1924, 315, 45.

2:Vt ?.Tack?, ;;.Link, :l.Ju;>;;i?ti, i ~ n ~ ; L.:rnst, Z. iistUrfGrSCh., T e i L 3, 1'336, 41, 1123; A.P.Coake,Jr. snd J.Yan Jaw, J. 3ry. &., 7 9 S , 51, 75::; J.?.iii Lvorth, J.tlanic!i, K.Krt.;5tct, J.'3cck, afit: J.Stra!iLe, J. drysnonet . Chilm., 1936, 315, C?.

2~15 J.T.g.II.Jast rzebsb;i, G.vin tccter:, C.T.i;nsap, A.r:.!':.!:chr<!urs, J .ilroun, drlc A.L.Spck, 3 r g s n o n e t a l l i c s , 1?3L, 5, 1551; D.:)aktirri ieks, L .F.rloskir;s, drid

C.L.RzLls, w. J. Chwi.,, I?::;, 39, 1221; O.A.RarnGboyc, T.T.r-juf.igl.~oy:, all(!

P.S.Hitrrison, L. d r s G e t . Chela., ' I%G, 305, 17; ,3. l :dLwt, ;I.& Jeso, anti :..I:archanli, ibic!, 299, 31'3; S.i<.Lci. and B.<.~lic:loLson, ibiJ, 339, 277; l : . ~ . i : o t ~ o y a n J . t i . P u r c e t t , w, 303, 179.

%;,I; G.C.!r;lc!cnleyctr, S .Kerscht, C.StaL'cr, anc! !:.:iorchLer, Spc'ctrochii i i . P,cta, P a r t - K , I?;:<>, 42, 1115; A.r:c>rcha?c!, P.GervaL, K.Rivi?r?-Zauai?t, G.Lacrdi;ipe, anL! .I.K\iat tzayoun, - i b i d , l w 5 , 41, 1C;II.

237 i:.S:;rke, L.Rosch, and R.Sclir,iutzLer, Phosghorus Sutghur, 1926, 27, 237; W . D . ;:otaz ne nk 0, A . V . Rut; s n, ,I. 2 . 3 r d pa i L ci, J n;' L . ti. !:a r k av s I( i i , Z I I . Ub s t i c ii . - Khii,]., 1725, 55, 2793 (3. &.# 'l?X, 105, 131242).

- - -- -, 1112.

--

----- - -

- --

-

- --

- 223 I,I.L.J.liackney and A.D.rlorman, J. Chei,i. Sot., Chcm. Conmun., 19:?j, J5C. 7 0 LO^ Fc . Appe I, C . Po rz, arid F . Knach, &-=TI W m l Y m ; I ? . Aiipe L ,

C.Casscr, F.Knoch, and 3.tlirmarir1, -, 2915.

S.PfLauiii, ib i r i , 41115.

(w. e., 13&6, 105, 791255); Z . I I ~ ~ C L , 3.Nirm;!nn, W.Schuiin, and F.Knoch, i'hngew. Chcm. fnt. e. Encjl., 1936, 25, 932.

1926, 25, 919; C.CuLcasi, ti.Gronc+ii, J.Escudie, C.Courct, L.PujuL, anC P.Tordo, J. Aner. Cherii. K., 1935, 108, 3131?, V.D.40rnisnenks, A.V.Ruban, S.V.I%ssnova, L.K.PoLyacIienko, and L.l!.Karksvskii, PliosPhorus SuLphur, 1935, 22, 365; V.D.t?omanenko, E.O.KLeSanskii, and L.tJ.Markovskii, E. - Obshch. -- Khia., 1935, 55, 2141 (a. *., 1956, 105, 420691').

\J.Rosch, U.Vogelbacher, T.Allspach, and :!.Rcgitz, J. Orgat loaf t . N., 1936, 306, 3Y; G.RarkL and H.Sejpka, Angeu. Chen. z. Ed. w., 1986, 25, 264 and T e t r a h e d r o n G., 1935, 27, 171 snd 1771.

234 K.IssLeib, ti.Schmibt, and P.Berymann, 2. Anorg. A L L % . Chela., 19S5, 529, 21.5; R.AppeL and R.:loors, Angew. Chem. z. @. a., 1936, 25, 567.

295 il.iippe1, J .knzcL, and F.Knoch, m. K., 1905, 118, 4008; R.AppeL, C.Casscr, and F.i<noch, ibiJ, 2699; P.PeLLor,, Y.Y.C.Yeung Lam KO, P.Cssquer, J.!laneLin, and R.Carrie, Te t rahedron w., 1956, 27, 4219.

236 R.Agpel, T.baitzsch, F.Knoch, arici G.Lenz, Chrtn. K., 191.k5, 119, 1977; R.Ag,pel, E .Gaitzsch, K.-Ii.Dunker, and F.Knoch, =, 535.

297 D.Sudat, E .lJiecke, Q.Krcbs, and M.Dartnann, C l i i m i a 1SY5, 39, 277; A . X . A r i f , A.H.Cowle;j, and S.Quashie, J. a. z., Chcm. Commun., 1886, 1437; R.ApyeL, V.Uinkhaus, and F.Knoch, %. Eer., 1986, 119, 246.5; b.Mark1, H.Sejpka, S.Diet1, O.IJubr, and M.L.Z=Ler, Angew. Chen. x. Ed. Engl . , 1936, 25, 1003.

299 G.Markt dnij G.Dorfmeister, Te t rahedron s., 13s?:~, 27, 4.419; I;.FfarkL and

291 Yu.A.Viets, S.G.tieyanova, and V.L.Foss, fi. Ohshch. Khin., 1386, 56, 715 -

213 P.Jutzi, 'J.iieyer, i'!.;:rebs, and ::.3artmann, Angew. m. 1. Ed. w.,

293 T.ALLspach, M.Regitz, 'i.Becker, and U.Uecker, Synthesis, 1926, 31;

298 Z F r i t z iifid R.I3iastocli, I . Anorg. A L l r j . Cht'ifi., 1356, 535, 63 arid 9 5 ;


299

3!;0 311 1

302

333

394

525

3%

53 7

3c!?

3C9

31 -!

51 1

31 2

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430

401

402

403

421

4?5 435

437

402

407

41 ;;

P.Ganis, G.Vall2, D.Furlani, and G.TagLiavini, J. Organmet . Chen., 1935, 302, 165; J.S.Ts.e, n.J.ColLins, F.L.Luc, and E.J.Gabe, c, 310, 169. G.U.Greyory, R.S.Arrfistron?;, il.J.Aroney, E.%.Picrens, and K.R.Skmp, e. - - Chem., 1986, 39, 221; K.Ueyarna, G.fJIatsubdyashi, R.Shimizu, and J. T.Tanaka, Polyhedron, 1985, 4, 1783. E .RivaroLa, F.Saiano, A.Fontana, and U.IIusso, J. Organornet. Chem., 1326, 317, 28s; R.J.F.Jans, G.van Koten, R.R.Andrea, K.Vrieze, A.L.Spek, E.Koj ic-Prouic, and J.L.de Doer, Recl . Trav. C i t j i t i . Pays-Bas, 19E6, 105, 317. A.I.Tursina, L.A.Aslanov, V.V.Chernys!iev, S.il.Fledvedev, and A.V.Yatsen%o, Koord. Khin., 1YY5, 11, 594 (%. z., 1936, 104, 129991); J.:f.Pliller, H.Tionda1, I .Uharf , and i;.Onyszchuk, -I. Orcanornet. Chela., 1936, 306, 193; ti.Fuji\.rdra, F.Sakai, Y.iiikdwa, and Y.Sasaki, Dull. C l i r m . z. Jpn., 1925, 58, 1741. J .U.SI:i'ncer, C.d.2elser, S .R.Floyer, K .E .Hai n ~ s , F?.A.DiSt rdvalo, and C.H.YoJer, Oraanometal l ics, 1984, 5, 113; T.A.K.Al-Allaf, J. Organmet . Chcm., 1336, 306, 337. T.P.iuckhart and I i .f.f*l~nders, I n c r y . Chm., 19d6, 25, 072. I n d i a n J. Chein. Sect.;$, 1925, 24, 873, 703, 2nd GI9 (E. &., 1726, 105, 203996, 172S5?, and 6 5 4 6 ) ; Polyhedron, 1735, 4 , I W S . J. OrCanomet. Chcni., 1386, 299, $1; 310, ZC5 and 25'3; 317, 153; Polyhedron, 192.6, 5 , 1227. I n o r g . Chin. Acta, 19Pb, 111, 157; 112, 41; J. Organcnct. Chen., 193S, 311, 327; J. z. Malays., 1325, 6, 39 (m. Aj., 1?13m5, 105, .'+EY73); I n d i a r i L. Chein. Sect.)., 1725, 24, 2311 (Cttein. At)s., 1926, 104, 34144) . Polytwdron, 15736, 5, 7449; I n d i a n J . C h ~ S e ~ . r \ , 1?25, 24, Y54 (z. - Ats., 1336, 105, 1C1279). 2 . Anorg. ALLb. LIZ., 19C6, 539, 2!'; i. Orjanoii iet. Cheii!., I%X, 303, 351.

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7 Group V: Arsenic, Antimony, and Bismuth

BY J. L. WARDELL

1 Tervalent Compounds

The synthesis, equation (1) and spectra ( 1 3 C n.m.r., 'H n.m.r., m.s.) o f the arsa- ethyne ( 1 ) have been reported.' Further examples' of cycloadditions to AsX

2,4,6-But3c6H2C(o)C1 + LiAs(SiMe3)2 5 2,4,6-BUt3C6H2C As (1 1 (1) m.p. 114-116°C

bonded compounds include the [3+21 additions of 1,3-dipoles to 1!-1,2,4 diaza-arsoles and the [2+4] additions of 1,3-dienes to F3CAs=CF2, generated s i t u by the thermolyses of Me3SnAs ( CF3) 2. - The synthesis of B u ~ ~ A s P = C ( S ~ M ~ ~ ) ~ was achieved3 from But2AsLi and (Me3Si)2C=P1. obtained by electron diffraction a t 74°C; the gas phase than in the solid state. ' results5 from treatment of Mes2SbBr with Mg. have been investigated in PhH solution.6

The gas phase molecular structure of R2SbSbR2 (2, R=Me) has been the Sb-Sb bond length i s shorter in

Compound [ 2 , R=2,4,6-Me3C6H2(Mes)l Exchange equilibria, equation (2 )

Me2MM& + Me2M'M'Me2 2Me2MM'Me2 2 ( M M' = P , As, Sb or Bi)

The mi xed metal compounds, 1 - (2,5-dimethyl arsolo) -2,5-dimethyl s t i bol e ( a

Compounds, thermochromic compound) and Pr2BiSbMe2' have also been investigated; in another study, attempts to i so la te R2SbMRI2 (M=P or As) failed. ' R2MMR2 (M=As, Sb or B i ) react9 with R'EER' ( E = S , Se or Te) to provide R2MER' (3); (3, E=Te) are thermochromic. Halogens and chalcogens cleave' the By-Bi bond in Pr2Bi-BiPr2.

Compound (4) , reacts with" PC15, Br or I 2 (Scheme 1 ) ; the spectra and

$ - 6 - MeC(CH2AsX213

I5 X=Cl BrorI l

AS -AS X / A s . A s A *

(4)

Reagents: i , PC15Br2 or 12; i i , ' excess PC15, Br2 or 12.

Scheme 1 .

properties of (5) and ( 6 ) as well as the crystal structure of (5, X=I) were reported.

[For references see p a g e 145 142

Group V: Arsenic, Antimony, and Bismuth 143

The fo l l ow ing homonuclear c y c l i c compounds have been synthesised:

[(PhSb)6.Ll (7,L=dioxane, PhH o r PhMe) from slow o x i d a t i o n ” o f PhSb(SiMe3)2 i n L, and [ ( M e ~ s b ) ~ . L ] ( ~ = 6 , L=PhH; Crysta l s t ruc tu res have been determined f o r the f o l l o w i n g metal-metal bonded species;

( i ) (7) : centrosymmetric S b i c h a i r s (Sb-Sb, mean 2.84 8 ) , Ph groups equator ia l , ” s h o r t Sb.. .Sb i n te rmo lecu la r distance, mean 4.20 R ; L i b r i d g e ” ButAsAsBut2 w i t h a p lana r Li2As2 core; and ( i i i ) ( d i ~ x a n e ) ~ L i A s P h ~ , (Et20)2LiAsPh2. [ ( 12-cr0wn-4)~Li 1 [SbPh2] .1/3THF (2-co-ordinate Sb) and13

[ ( 1 2 - c r o ~ n - 4 ) ~ L i I [Sb3Ph41 .THF.

complex Ar3Bi.S03, as repo r ted e a r l i e r ;

g i ve ArnBi(OSOpR)3-n(n=l o r 2).

( i ) [K(18-crown-6)] [(PhSb12)41] (an ion cons is t s o f a c e n t r a l I- co-ord inated t o

4 PhSb12 u n i t s i n a square p l a n e ) ; 1 5 ( i i ) Ph2SbOP(X)Ph2 (X=O o r S ) (chains v i a b r i d g i n g l igands; pseudotr igonal b ipyramidal Sb); l6 ( i i i ) [Ph2SbSM(S)Ph212

(M=P o r As) (Sb2S4M2 r i n g s w i t h -annular Sb.. .S i n te rac t i ons ; d i s t o r t e d square pyramidal Sb);” ( i v ) Ph2Sb-8-quinol inethiolate ( che la t i ng l i gand : d i s t o r t e d pseudo-octahedral Sb),” ( v ) P ~ S ~ ( S A C ) ~ : [ che la t i ng l igand; d i s t o r t e d

square pyramidal Sb;

weak dimers 1, l9

[7.3.1.1 3,7]-tetradecane, obta ined on h y d r o l y s i s o f 12As(CH2)3As12 (As504 core) .20

The v i b r a t i o n a l spect ra have been repor ted f o r PhM(SCH2CH2)2X (n=l , M=Sb o r B i ; X=O o r S).’l Macrocycles con ta in ing As-S l i n k s have been synthesised, e.9. P ~ A S S ( C H , ) ~ S A S ( P ~ ) ( C H ~ ) ~ C H ~ and P~AsS(CH,)~O(CH~)~SAS( Ph)(CH2)20(CH2)2, from approp r ia te ch loroars ines and d i t h i o l s As and P have been r e p ~ r t e d , ’ ~ 3. But2As-N=S=NP(X)But2 (X=S, Se o r Te).

n=4, L=PhMe) from5 MesSbBr2 and Mg.

( i i ) [(THF)LiButAsAsBut2I2:

Sulphur t r i o x i d e reacts14 w i t h A r 3 B i t o g i ve Ar2BiOS02Ar, and n o t the

RS03H a l s o cleaves the Ar-Bi bonds t o

The c r y s t a l s t ruc tu res o f the f o l l o w i n g compounds have been determined:

i n te rmo lecu la r Sb.. .S i n t e r a c t i o n s (3.802 8) l ead ing t o and ( v i ) 2,8,13,14- t e traoxa-1 ,3,7,9- t e t r a - a r s i n e t r i c y c l o -

Mixed su lphur di imides, con ta in ing

2 Quinquevalent Compounds

Thermolysis o f Ph5Bi i n C02 prov ided24 Ph3BiOC(0)C6H4-~. s tudy o f Me3SbC12.SbC13 (8) has been c a r r i e d out; were re la ted ” t o the known c ross - l i nked chain s t r u c t u r e o f ( 8 ) .

( 121Mdssbauer, ’H n.m.r. and I 3 C n.m.r.) o f R3SbX2were i n t e r p r e t e d z 6 as r e v e a l i n g t h a t as the e l e c t r o n e g a t i v i t y o f X increases, the e l e c t r o n c loud about Sb spreads towards X and a l so towards the p lane perpendicu lar t o the Sb-X a x i s .

f l u o r i n a t i o n o f R3As (R=C6F5) and ( i i ) by anodic o x i d a t i o n o f R3As i n the

presence o f C5H1 1NH2 and pyH+,BFi.

An e.s.c.a./n.q.r. the observed n.q.r. t r a n s i t i o n s

Spectra

Preparations” o f R3AsF2 have been achieved ( i ) by low temperature d i r e c t

Urganometallic Chemistry

Crystal s t ructures have been determined f o r ( i ) (C6F5)3AsF2 ( t r igona l b i ~ y r a m i d a l ~ ’ ~ As); ( i i ) (Ph3SbO)2 (Sb202 core2”); ( i i i ) Ph3SbOCMe200, obtained2” by ox ida t ion o f Ph3Sb by H202 i n Me2CO);

M=Sb o r B i ) ( t r i g o n a l bipyramida12’ M; weak M...O i n te rac t ions) ; ( v ) [Ph3Sb(OSO2R)I20 (R=Ph o r CF3) ( t r i g o n a l bipyramidal 3 0 Sb) and ( v i ) [Pr3AsNH2]C1

(near te t rahedra l 3 1 As).

reported.

an i o n i c s t ruc tu re (from v ib ra t iona l ~ p e c t r a ) . ~ ’

e lec t ron ic spectra o f R3SbQ2 (10) and R3SbQX (11, X=C1 o r Br) (Q=8-quinolinate), i t has been deduced32 t h a t Q has a greater chelat ing e f f e c t i n (11) than i n (10).

have been

( i v ) Ph3M(OS02Ph)2 (9,

Syntheses and spectra o f o ther [R3AsNR1R2]C1 were a lso

I n contrast t o covalent ly bonded (9), MeSSb(OSOR)2 (R=CF3 o r CH2CH20H) has From the n.m.r. and

Stable y l ides, Ph3?b-cXY ( e 2 . X,Y=pMeC6H4SO2,PhCO,MeCO; XY=-C(O)( CH2)3C(0)- by the reactions o f Ph3Sb and XYCN2 i n the presence o f

CU [CH( COCF3)2]2.

3 Uses i n Organic Synthesis

The reactions o f R NH2 w i t h Ph3Sb(OCOR)2 prov ide34 good y i e l d s o f RCONHR ; i n addi t ion amidation o f RC02H by R NH2 i s catalyzed by organoantimony compounds. Barton and coworkers 3 5 have repor ted on ( i ) the copper-catalyzed N-aryla t i o n o f

amines by Ar3Br(OCOR)2; ( i i ) the copper catalyzed 2-phenylat ion o f phenols and

enols by organobismuth ( v ) species and ( i i i ) the cleavage o f a-g lyco ls by the combination: Ph3Bi, N-bromosuccinimide, K2C03, CH3CN and H20.

4 Bibliography

P. de Meester, S.S.C. Chu,and T.L. Chu, Acta Crystal logr . , Sect. C, 1986, 9, 25.3. Crys ta l s t r u c t u r e of 10-(~-tolyl)-5,10-dihydrophenassazine.

V.A. Yablokov, I . A . Zelyaev, E.I. Makarov, Yu.A. Gatilov, V.A. Gomina, and A.D. Zorin, Zh. Obshch. Khim., 1986, 56, 365. the gas phase.

G. Xu, J. Zhou, and Y. Tang, Wuli Huaxue Xuebao, 1985, 1, 6.

T.T. Vinh and B. Munson, Org. Mass. Spectrom., 1986, 2, 41. Proton a f f i n i t i e s of Ph3M by reac tan t ion monitoring.

A.V. Gushchin, T.G. Bri lkina, and V.A. Dodonov, Zh. Obshch. Khim., 1985, 55, 2630.

Z.U. Panfi lovich, N.R. Ivanova, K . I . Kuzmin, and I .P. Lipatova, Zh. Obshch. Khim., 1986, 56, 124. HCZCAs(R)CXR’R20H.

V . I . Gavrilov, R.R. Rakhmatullin, Zh. Obshch. Khim., 1985, 55, 1016. Kinet ics of reac t ions of phenoxa-arsines with MeI.

Thermal decomposition of R3AS i n

Photolysis of Ph3M.

Reaction of Ph3Bi with PriOH and CU(OAC)~.

J . M . Chehayber and J . E . Drake, Inorg. Chem. Acta, 1986, 112, 209. [MenAsH3-n]-

BX3. - -

Group V: Arsenic, Antimony, and Bismuth 145

N.A. Chadaeva, F.G. Khal i tov, L.V. Awa-Kumova, and R.R. Shag idu l l in , Zh. Obshch. Khim., 1985, 55, 2293.

M. Geoffroy, A. L l ina res , and S.P. Mishra, J. Chem. SOC., Faraday Trans. 1, 1986, 82, 521. E . s . r . spectrum of Ph AsI.

X. Lu, Q. Wang, X. Tao, J. Sun, and G.Ei- , Huaxue Xueboa, 1985, 43, 450. Reduction of Ph3As0 t o PhjAs, 9 using (PhO)3P.

B.A. Abalonin, L.A. Lakhotskaya, and Yu. F. Gat i lov, Zh. Obshch. Khim., 1986, 56, 830. Decomposition of Et3As(SEt)I.

P. Raj, A.K. Saxena, K. Singhal , and A. Ranjan, Po l hedron 1985, 4, 251. Formation of (C6F5)3SbXY (X,Y=I, C 1 ; I, N3; NC*-' v.V. Sha ru t in , V.T. Bychkov, Yu.N. Saf'yanov, E.A. Kuzmin, and R.P. Zakharova, Zh. Obshch. Khim., 1985, 55, 1652.

F.D. Yambushev and G . I . Kokorev, Zh. Obshch. Khim., 1986, 56, 484, 485. Oxidation of A r 2 E t A s by peroxides .

I. Haiduc and C. S i l v e s t r u , Inorg. Synth., 1985, 23, 194. Synthesis of Ph2SbC13 from Ph4Sn and SbC15.

G . I . Kokorev, F.D. Yambushev, and S.V. Kutin, Zh. Obshch. Khim., 1986, 56, 482. A r A s C 1 4 .

ArAs(OR)2.

3

(cymantrenyl)3SbX2.

C. Sun, M. Sh i , and R . J i , Yiyao Gongye, 1985, 16, 402. C02H.

p-(HO)2Sb(0)C6H4CHNH2-

V.S. Gamayurova, N.A. Niyazov,and F.G. Khal i tov, Zh. Obshch. Khim., 1985, 55, 2493.

K. Pandey and R.C. Smivastava, Synth. React. Inorg. Met- Org. ,Chem., 1985, 15, 327.

L.B. Ionov, S.M. Reshetni tov, L.L. Makarova, and T.M. Flegontrova, Zh. Obshch. Khim., 1985, 55, 862. RR'As(0)-0-menth.

T. Kauffmann, R. Joussen, and A. Woltermann, Chem. Ber., 1986, 119, 2135; T. Kauffmann, G. Kieper, and N. K l a s , w., p.2143. Ph2As(0)CRR'Li and Ph3As(0)CRR'E.

W. Ding and X. Kong, Huaxue Xuebao, 1986, 44, 255. Reaction of Ph As=CHBz and RC3C02Me.

W. Tao and H. Pu, Huaxue Xuebao, 1985, 43, 487. Reactions of Ph3As=CHCOR wi th PhN3.

Reaction of Ph3As0 and H02C(CH2)GC02H.

Synthesis of (Ph3SbX)20 (X=02CR, ON=CRR' ) .

3

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G. M r k l and H. Sejpka, Angew. Chem.,Int. Ed. Engl., 1986, 25, 264. G. M r k l and H. S e i t z , Tetrahedron L e t t . , 1986, 27, 2957; J. Grobe and D. Le Van, J. Organomet. Chem., 1986, 311, 37. 0.1. Kolodyazhnyi, I . V . Shevchenko, and V.P. Kukhar, Zh. Obshch. Khim. , 1985, 55, 1862. A. Csaszar, L. Hedberg, E.G. Ludwig, and A . J . Ashe, Organometallics, 1986, 2, 2257. M. Ates, H . J . Breunig, A. Soltani-Neshan, and M. Tegler , Z . Naturforsch., T e i l B, 1986, 41, 320. A . J . Ashe and E.G. Ludwig, J. Organomet. Chem., 1986, 303, 197. H . J . Breunig and D. mller, Z. Naturforsch., T e i l B, 1986, 41, 1129. J . G . Stevens, J . M . T roos t e r , H.F. Martens and H.A. Meinem, Inorg. Chem. Acta, 1986, 115, 197.


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-

-

(b) O.V. Parakin, E.V. N i k i t i n , Yu. A. Ignat’ev,

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8 Metal Carbonyls

BY B. J. BRISDON

1 I n t r o d u c t i o n

The format o f t h i s r e p o r t i s s i m i l a r t o t h a t used prev ious ly , w i t h r e l e v a n t reviews noted below and papers from the pr imary j ou rna ls considered i n t h e i r

most appropr ia te sect ion. and consequently emphasis has been placed on the synthesis, s t r u c t u r e and reac t -

Space requirements have necess i ta ted some s e l e c t i v i t y

i v i t y o f new metal carbonyl species a t t he

chemi s try.

Several very i n fo rma t i ve reviews have

Advances i n Organometal l i c Chemistry. o f o r g a n o w t a l l i c sonochemi s try, together

t r a n s i e n t organometa l l ic species by f a s t t

expense o f t h e i r sur face immobi 1 i s e d

been publ ished i n Volumes 25 and 26 o f

The former conta ins a t i m e l y account

w i t h a r t i c l e s on the de tec t i on of me-resolved i n f r a r e d spectroscopy,2

and on the chemistry o f carbonyl d e r i v a t i v e s o f T i , Z r and Hf .3 volume comnences w i t h a rev iew of O s g c l u s t e r chemist ry4 and a l so conta ins an a r t i c l e on some s p e c i f i c photochemical reac t i ons o f metal carbonyl derivative^.^ Bonding i n molecular c l u s t e r s and t h e i r r e l a t i o n s h i p t o bu l k metals has been

reviewed,6 and the use o f computer graphics i n the study o f metal c l u s t e r com-

pounds d e ~ c r i b e d . ~ t r a n s i t i o n metal polyhedra,8 and t o s u b s t i t u t e d ruthenium carbonyl ha1 ides ,9 were a1 so pub1 ished i n 1986. t i o n o f t r a n s i t i o n metal c l u s t e r carbonyls i n the gas phase,1° and the r o l e ’ o f

e l e c t r o n t r a n s f e r , t r a n s i e n t r a d i c a l s and i o n r a d i c a l s i n metal carbonyl

chemistry.” Relevant ma te r ia l i s a l so i nc luded i n the Proceedings o f t he Climax 5 th I n t e r n a t i o n a l Conference on the Chemistry and Uses o f Molybdenum which a r e publ ished i n Polyhedron, and the Plenary and Sect ion l ec tu res presented

a t t h e Twe l f t h I n t e r n a t i o n a l Conference on Organometal l ic Chemistry which appear i n Pure and Appl ied Chemistry.12

Na2[ Fe2 ( CO) 8 1, Na2 [Fe3 ( CO) 1 11, [ PPN12 [ Fe3 (CO) 1 1 1, EtJ[Ru3H (CO 1 1 1 1, and Au (CO) C1 a re descr ibed i n Volume 24 o f Inorganic Syntheses. l3

The l a t t e r

Long a r t i c l e s devoted t o c l u s t e r complexes con ta in ing opened

Other t o p i c s surveyed inc lude the photofragmenta-

The preparat ions o f Na2[Fe(C0)4],

2 General and Theoret ica l Studies

A much g rea te r understanding of t he reac t i ons o f l i g a t e d CO has been obta ined as a r e s u l t of a number of s tud ies f rom d i f f e r e n t l abo ra to r ies . I n an

impor tant t h e o r e t i c a l paper, the na tu re of CO reduc t i on by dimolybdenum and



di tungsten centres has been explored w i t h the a i d of Fenske-Hall ca l cu la t i ons .

The r e a c t i o n sequence represents a stepwise reduc t i on i n M-M and C-0 bond order

and i s suggestive o f a model f o r t he r e a c t i o n pathway o f CO on a metal ox ide

surface.14 Reductive coup l i ng o f CO t o form a new k i n d o f CO-derived product, Me3SiOCzCOSiMe3, s t a b i l i s e d by co-ord inat ion t o Ta(1) has been and a

mechanist ic study c a r r i e d ou t on the r e a c t i o n by which a c t i n i d e d i a l k y l s undergo double carbonylat ion and C-C bond format ion t o y i e l d complexes o f the cis- RC(O)=C(O)R 1igand.l6 The complex [Fe(CO)Cp(PMe3)Me] has been shown t o undergo homologation on successive treatments w i t h CO and BH3.THF t o g i ve a f t e r f o u r

carbonylat ions [Fe(CO)Cp(PMe3)(COBu)], which on ox ida t i on y i e l d s e n t i r e l y CO- der ived pentanoic acid.17 The mechanisms o f CO hydrogenation,18 and CO i n - s e r t i o n reac t i ons ,19 have been f u r t h e r i nves t i ga ted .

A reac to r system and techniques f o r per forming p repara t i ve sca le metal

vapour synthes is experiments us ing “non-condensable’* 1 igands have been des- c r i bed,20 and the v i a b i 1 i ty o f the method demonstrated by the s ing le-s tep

syntheses of V(CO)6, Cr(C0)6, Ru(C0)5, Mn2(CO)lo, Fe3(C0)12 and Ru3(C0)12. f i r s t example o f a metal complex con ta in ing bo th CO and a te rm ina l 0x0 l i g a n d

has been claimed,21 and evidence presented f o r the format ion o f t he f i r s t mole- c u l a r a c t i n i d e complex o f CO, i n s o l u t i o n and s o l i d phase.22

c a t i o n i c metal carbonyl complex [Co(CO)Cp(diphos)12+ has been prepared and the unprecedented e l e c t r o p h i l i c i t y o f t he CO l i g a n d explored.23 r e a c t i v e nuc leophi les such as a n i l i n e and h igher a l coho ls r e a c t t o y i e l d a r y l -

carbamoyl and carboal koxy compounds respec t i ve l y . Transformation of a terminal

t o a b r i d g i n g CO l i g a n d accompanied by M-M bond cleavage has been observed, pro- v i d i n g an example o f t ransmiss ion o f e l e c t r o n i c e f f e c t s from one metal cent re t o

and the f i r s t complex con ta in ing the {P t3 (~3 -CO) l moiety has been

described, so extending the analogy between carbonyl c l u s t e r s and CO adsorpt ion

on surfaces.25 I n t e r e s t i n the bonding o f metal carbonyl species which can be

regarded as prototypes f o r CO chemisorption on metal surfaces continues.26 Bonding and s t r u c t u r a l s tud ies have been publ ished on M(CO), moiet ies (M = V,

M = A l , 3: = 2;34 M = Ga, x: = 235) as w e l l as on s tab le molecular c a r b o n y l ~ ~ ~ and n i t r ~ s y l s . ~ ~

and symne t r i ca l l y b r i d g i n g CO groups i n 47 compounds have been subjected t o a

d e t a i l e d q u a n t i t a t i v e analys is , and cu r ren t bonding models discussed w i t h re ference t o these data.38 A sur face force f i e l d model f o r the molecular mechanics s imu la t i on o f l i g a n d s t ruc tu res i n t rans i t i on -me ta l carbonyl c l u s t e r s has a l so been developed,39 and ca l cu la ted s t e r i c energies fo r a range o f car- bony1 c l u s t e r s have been c o r r e l a t e d w i t h M-M separations. I n an impor tant t h e o r e t i c a l paper, t he bonding i n octahedra l c l u s t e r s w i t h face- and edge-

b r i d g i n g l i gands has been examined us ing semi-empir ical MO ca l cu la t i ons , and

The

The new, d i -

R e l a t i v e l y un-

2 = 1-3;27 M = Fey x: = 1;28,29 M = N i , 3: = 1;29,30 M = Cu, 3: = 1 o r 3 5 9 9 3 1 - 3 3

S t r u c t u r a l data f o r t e rm ina l , l i n e a r and bent semibridging,

Metal Carbonyls 149

the c lose r e l a t i o n s h i p demonstrated i n the e l e c t r o n i c s t ruc tu res o f c l u s t e r s w i t h a-donor and r -acceptor l i g a n d ~ . ~ ~

s i x apex metal carbonyl c l u s t e r s has a l so been proposed based on a comparison

w i t h cZoso-borane c l u s t e r s . 41 The 1 i k e l y d i f f e rences between polyhedra l re -

arrangements i n c l u s t e r u n i t s and l i g a n d in terchange i n co-ord inat ion compounds have been assessed.42 For the former systems a mechanism i n v o l v i n g the succes-

s i v e break ing and reforming o f s i n g l e edges i s p r e f e r r e d on energe t i c considera- t i ons .

c l u s t e r s have been measured d i r e c t l y i n a powder sample us ing Four ie r t rans -

format ion o f the X-ray d i f f r a c t i o n pat tern,43 and the p o s s i b i l i t y o f apply ing the RDF method more genera l l y i s discussed. h igh n u c l e a r i t y metal c l u s t e r s have appeared, some o f t he r e s u l t s of which a re

o f relevance t o the i n t e r p r e t a t i o n o f cluster-beam experiments, as w e l l as

aspects o f c a t a l y s i s and sur face science. 44

3 Chemistry o f Metal Carbonyls

The e l e c t r o n i c s t r u c t u r e of closo-

The d is tances between the heavy atoms o f s i x model organometa l l ic

Fur ther t h e o r e t i c a l treatments of

3.1 Mononuclear Carbonyl Derivatives.-Several un re la ted s tud ies on the redox chemistry o f mononuclear metal carbonyls have been described. Carbonyl-

me ta l l a tes o f C r , Mo, W , Mn and Co were a l l ox id i sed by V(CO)6 t o n e u t r a l

species, and l a b e l l i n g experiments i n d i c a t e d an ou te r sphere mechanism f o r t h e

V(CO)6-[Mn(CO)5]- react ion.45

Cr(C0)6 has shown t h a t con t ra ry t o some prev ious repo r t s , [Cr(CO),]+ i s formed i n CH2C12 s o l u t i o n under app rop r ia te condi t ions. t h e s i s i n g chromium carbonyl f l u o r i d e complexes us ing e lect rochemical procedures

was a l s o explored i n t h i s study.46 The redox r e a c t i v i t y o f photogenerated

Cr(C0)5 has been described,47 and a d e t a i l e d re-examination of t he e l e c t r o - chemist ry o f mononuclear and b inuc lea r manganese carbonyl species has shown t h a t t he 17-e lect ron Mn(C0)S r a d i c a l i s a key in termediate i n such p r o c e s s e ~ . ~ ~

However, the importance,of 19-e lect ron species has been st ressed i n r e p o r t s on the e lec t ro reduc t i on o f Cr(C0)6, [Mn(CO)6]+ and Fe(CO)5.49,50 The r a d i c a l

anions [Cr(C0)6]' and [Fe(CO)5]r undergo f a c i l e hydrogen atom t r a n s f e r w i t h

t r i a l k y l t i n hydr ides t o y i e l d formyl metal in termediates, which i n t u r n are sub jec t t o chain decomposition l ead ing t o the corresponding hydrido-metal en ti t i e s . 49

A r e i n v e s t i g a t i o n o f the e lec t rochemis t r y o f

The p o s s i b i l i t y o f syn-

The t r a n s i e n t i n f r a r e d absorpt ion spect ra o f the co -o rd ina t i ve l y unsatur-

The r e s u l t s i n d i c a t e t h a t

a ted Cr(CO), species (z = 5, 4, 3 and Z ) , generated v i a excimer l a s e r photo-

l y s i s of gas phase Cr(C0)6, have been d e ~ c r i b e d . ~ ~ the gas-phase s t ruc tu res of these species a r e s i m i l a r t o those observed i n condensed-phase experiments. Reactions, i n c l u d i n g some k i n e t i c data, have

been repor ted on severa l o'f these Several photolyses experiments

have been c a r r i e d o u t on and r a t e constants f o r t he r e a c t i o n o f

Fe(CO), (n = 4, 3 o r 2 ) w i t h CO determined.57 The generat ion and some reac-


t i o n s o f t he 13- and 14-e lect ron e n t i t i e s [Fe(C0)2]; and [M~I(CO)~]- have a l s o been descr i bed.5e Gas phase ion-molecule reac t i ons between Fe(C0)5 and an extens ive se r ies o f anions (X') have been inves t i ga ted us ing a f l o w i n g a f te rg low

apparatus operat ing a t 300 K. Reaction genera l l y proceeds by n u c l e o p h i l i c

a d d i t i o n t o a f f o r d [F~(CO)L+{C(O)X>]', [Fe(CO),X]- and [Fe(CO)3X]' anlons. 59 A

u n i f i e d mechanism f o r gas-phase negat ive i o n condensation reac t i ons o f Fe(C0)5 has been pos tu la ted based on these experiments.

react ions i n v o l v i n g "bare" and so lvated anions w i t h Fe(CO)5 have a l so been made.6O Photo lys is s tud ies on Ni(C0)4,61 benzene so lu t i ons of O S ( C O ) ~ ~ ~ and [Co(CO)3(NO)] i n the gas phase63 have been c a r r i e d out . The n i t r o s y l d e r i v a t i v e d i ssoc ia tes

by a se r ies o f sequent ia l l i g a n d e l i m i n a t i o n s t o g i ve predominantly CoCO, which

reac ts w i t h parent [Co(CO)3(NO)] t o form a b inuc lea r species [CO~(CO)L+(NO)] of

unknown s t ruc tu re .63 and Ni(CO)I, have a l so been described and compared w i t h those o f o the r metal

carbonyl s . 3.2 Binuc lear Carbonyl Der ivat ives. -Fur ther r e p o r t s on the pho to l ys i s o f

Mn,(CO) 10 have been published. 65-69 D i r e c t de tec t i on via t r a n s i e n t i n f r a r e d

spectroscopy o f Mn(C0) 5 r a d i c a l s produced via l a s e r pho to l ys i s o f a gas-phase sample o f Mn2( CO) 1 0 have been and the e f f e c t o f e x c i t a t i o n wavelength on the two pr imary processes (Mn-Mn bond cleavage and d i s s o c i a t i v e l o s s o f CO)

has a l so been establ ished. 67 Further evidence t h a t 19-e lect ron species a re key in termediates i n photochemical d i sp ropor t i ona t ion of Mnz(C0) 10 w i t h amines and oxygen-donor 1 igands has been presented,6a and the mechanism o f the photo-

chemistry o f Mnn(C0)lo i n the presence o f quinones explored.69 the Mn-Mn bond s t reng th i n Mn2(CO)lo i n s o l u t i o n has been obtained, us ing

pulsed t ime resolved photoacoustic ca lo r ime t ry . 70

ment w i t h data obta ined v i a k i n e t i c measurements. The redetermined s t r u c t u r e

of MnRe(C0)lo shows a Re-Mn d is tance of 2.909(1) A, which i s cons iderably

sho r te r than t h a t repo r ted p r e v i o u ~ l y . ~ ~ The synthes is o f MnRe(C0)lo t h a t i s s p e c i f i c a l l y l a b e l l e d w i t h 13C0 on Re has been reported. CO exchange and f o r a h igh b a r r i e r t o m ig ra t i on of CO across the non-bridged Mn-Re bond has been obtained.72 ma t r i x i s o l a t i o n and t ime-resolved i n f r a r e d s tud ies on the photochemistry o f

M n R e ( C o ) ~ o . ~ ~ and reac t i ons .of Fez( CO)8 .74

[CrFeH(C0)9]- and [WFeH(CO)g]- a l l con ta in te rm ina l CO l i gands and a Fe-M

(M = C r o r W ) bond which may be viewed as a metal donor-acceptor bond.75 fu r the r r e p o r t on the preparat ion o f CoRh(CO)7 from e i t h e r the low temperature reac t i on o f [Rh(CO)Cl], w i t h [Co(CO)4]- i n the presence o f COY o r from

CozRh2(CO)iz and CO under pressure, has been published. on l y below -65 0C.76

Comparisons between analogous

The ion-molecule r e a c t i o n chemist r ies of [Co(CO)3(NO)]

An est imate o f

The r e s u l t i s i n good agree-

0

Evidence f o r pa i rw ise

A CO br idged species has been i d e n t i f i e d i n

S i m i l a r techniques have been used t o i n v e s t i g a t e the s t r u c t u r e

The he te rob ime ta l l i c carbonyl anions [CrFe( CO)9]2-,

A

The product i s s t a b l e

Metal Carbonyls 151

3.3 Polynuclear Carbonyl Derivatives.-Variable temperature MAS 1 3 C n.m.r. methods have been used to probe the exchange processes occurring i n solid homonuclear carbonyls containing 3 and 4 metal atom^.^^,^^ investigation of the chemistry result ing from both continuous- and flash- photolysis of Ru3(C0)12 has been carried carbonyl , IRu(C0)4)n, prepared from t h i s precursor.80 e f fec ts i n associative substi tution reactions of Ir4(CO)12 have also been examined.81 The combination of two Os3 units t o yield an improved route t o Os6 ra f t - l ike c lus te rs has been achievedYa2 and a comprehensive analysis published on the d i f fe ren t Mg cores o f stacked M3 t r iangles in the [Mg(CO)18]2'

(M = Ni or P t ) and [Rh~(C0)19]~' anions.83 134 electron [Rhlo(C0)21]~- anion has been described. example of a compact close-packed decanuclear species without an i n t e r s t i t i a l atom.84 Detailed variable temperature magnetic measurements on high nucleari t y platinum carbonyl c lus te rs have revealed a connection in properties between large platinum c lus te rs ( P t g - P t 3 8 ) and small platinum c r y s t a l l i t e s (ca. P t 4 0 0 ) . ~ ~

The preparations , s t ruc tures and reactions of several heteronuclear c lus te r

A quantitative

and a new polymeric ruthenium The s t e r i c and electronic

The synthesis and structure of the This i s the f i r s t

carbonyls have formed the subject of several publications. Reaction of [Ru(C0)3C12]2 with [Fe(C0)1+1~- in the presence of aqueous H ~ P O I , affords

reaction of Fe2Ru(C0)12 with [Fe3(C0)11I2- y ie lds Fe~,Ru2(C0)22, which was shown by X-ray analysis to contain a metal core of two Fe2Ru triangles joined by a Ru-Ru bond.87 However, reaction of [Fe3(C0)11I2' with [Fe2Rh(CO)lo]- y ie lds the [Fe3Rh3(C0)17I3- anion which contains a Fe2Rh3 trigonal bipyramidal metal core, with a dangling Fe atom attached to a Rh atom i n an apical s i t e . 8 8 An interesting ser ies of mixed Fe-Cu carbonyl c lus te rs have been isolated from reactions of [Fe(C0)4l2- with Cu(1) species.89 and [Fe~,Cu~(C0)16]~-. has been characterised crystallographical ly , and the preference of P t fo r c lus te r s i t e s of high metall ic connectivity noted.g0

*Fe~Ru(C0)12 together with [ H z F ~ ~ R u ~ ( C O ) ~ ~ ] and [ H ~ F ~ R U ~ ( C O ) ~ ~ ] . ~ ~ Further

Products include [ F ~ ~ C U ~ ( C O ) ~ J * The new Pt-Rh carbonyl c lus te r dianion [PtRhe(C0)19]2-

Heteronuclear c lus te r carbonyl containing non-transition metals aroused considerable i n t e r e s t i n 1986. structure of [Bi4Fe4(C0)13]2-, which was described in the previous report in t h i s se r ies , t h i s electron-rich Zintl-metal carbonylate has now been the subject of a detailed theoretical discussion.gl The attempted alkylation of a bridging CO in a c lus te r tha t also contains a Bi atom has been reportedYg2 and e f f o r t s made t o synthesise further Zintl-metal carbonylates by reaction of Bi2Fe3(CO)g with other metal carbonylates. of [ Fe3 (CO)9( IJ-H)~ (p3-Bi ) ] ,92 Ett+N[Bi2Fe2Co( CO) were elucidated by X-ray methods. electron-deficient species (Et4N)6[T16Felo(C0)36] has been described and the

Following the preliminary account of the

In the course of these studies, the s t ruc tures and (EtbN)2[Bi2Fet,( CO) 13 Ig3

In related studies the structure of the


bonding o f the anion discussed.94

Fe2(CO)8] was discovered dur ing attempts t o in t roduce Pb i n t o Z i n t l - t y p e c lus te rs .95 Several o the r syn the t i c and s t r u c t u r a l repo r t s on c l u s t e r carbonyls con ta in ing non- t rans i t i on metals are l i s t e d i n reference 96.

4 C lus te r Carbonyls Containinq C, N, P, As, S, Se o r Te

The s t r u c t u r e o f [Ru~+C(C0)13], prepared from [RugC(C0)15] v i a a s i x s tep

sequential synthes is , has been shown t o be s i m i l a r t o t h a t o f the analogousi ron c l u s t e r Y g 7 and by use o f MO c a l c u l a t i o n s and the polyhedra l s k e l e t a l e l e c t r o n p a i r approach, d i f f e r e n t e l e c t r o n counts f o r square pyramidal carbido-carbonyl c l u s t e r s have been a n a l y ~ e d . ~ ~ w i t h the a d d i t i o n o f l i gands t o small c l us te rs , the importance o f i n c l u d i n g the

d i s t o r t i o n o f the me ta l - l i gand core i n the c a l c u l a t i o n has been emphasised, as deformation o f a metal framework can occur i n some systems w i t h r e l a t i v e l y l i t t l e expenditure o f energy.99 Fur ther s tud ies on the reac t i ons o f [Fe~C(C0)15] and

on the e lec t rochemis t r i es of the [ F ~ ~ c ( c O ) ~ ~ I ~ - , [ c o 6 c ( c o ) ~ 5 1 2 ~ ~ [Rh6C(Co),512' and [co8c(co)18]2- i ons have been repo r ted and d i f f e rences i n behaviour of t he

anions re- la ted t o s t r u c t u r a l v a r i a t i o n s . l o O The a c t i o n o f heat on a THF s o l u t i o n o f [ c o ~ c ( c O ) ~ ~ ] ~ - r e s u l t s i n co l oss and formation o f t he [ c o 6 c ( c o ) ~ ~ ] 2 '

anion , lol which i s n o t i s o s t r u c t u r a l w i t h the i s o e l e c t r o n i c congener

[Rh6C(Co)13]2-. invest igated. i n so lu t i on . l o2 Treatment o f t he te t racapped [OS~OC(CO)~L,]~- d ian ion w i t h AuBrPPh3 and AgC104

y i e l d s [Osl oC( C0)21,AuBr]- which , on standing , a f f o r d s [OS~OAU( C)2( C0)~,8]~' i n h igh y i e l d . The Hg analogue can be prepared i n a s i m i l a r manner and pre- l i m i n a r y X-ray data on both these species have been repo r ted . l o3

[Ni6(CO)12]2' w i t h hexachloropropene i n THF y i e l d s [Ni38(C0)42C~]~ ' .

monoprotonated penta-anion conta ins a N i 3 2 C 6 i nne r core c l o s e l y r e l a t e d t o a fragment of the s t r u c t u r e of Cr23C6.1°4

[Co,N(CO),5]- i o n by thermal decomposition i n b o i l i n g THF, conta ins an octahedral m e t a l l i c c l u s t e r w i t h the N atom a t t he centre.105

l i g a n d d i s p o s i t i o n s d i f f e r from those o f [co6c(co)13]2-. p ro tona t ion of t h ree te t ranuc lea r n i t r i d o c l u s t e r s having a b u t t e r f l y metal geometry has been repor ted. The f i n a l products are h y d r i d o - n i t r i d o c lus te rs ,

but in termediates con ta in ing the imido l i g a n d can be trapped by C0.lo6 A lka l i ne p y r o l y s i s of [Rh6N(CO)1~]' leads t o t h e format ion o f [Rh12H(N)2(C0)23]3- which

contains a novel i r r e g u l a r dodecanuclear me ta l l i c skeleton.lO7 The [os6P(co)18]- anion conta ins a f u l l y encapsulated P atom and i s formed on thermolys is o f [Os6H( PH)(CO)21]' i n toluene. lo8

conta in ing metal carbonyl c l u s t e r s have a l so appeared.log

The h igh y i e l d synthes is o f [PbIFe(C0)4)2-

I n es t ima t ing the s t r a i n energy associated

The r e a c t i o n o f [Re7C(CO)21]3- w i t h e l e c t r o p h i l e s has been

One o f the products, [HRe7C(CO)21]2', e x i s t s i n isomer ic forms

Several rou tes t o h igh n u c l e a r i t y c l u s t e r s have been explored.

Reaction o f The

The new anion [CogN(C0)13]-, obta ined from the t r i g o n a l p r i s m a t i c

The remaining A study o f t he

S t r u c t u r a l r e p o r t s on p4-P and p4-As

Metal Carbonyls 153

An i n t e r e s t i n g communication on t h e synthes is of t he f i r s t i s o l a b l e i r o n carbonyl d e r i v a t i v e s obta ined d i r e c t l y from an {Fe~+S~+}-c luster and CO has been

pub1 ished, and the s t r u c t u r e o f one product, [Fe3S(CO),I2-, has been determined

by X-ray methods. Also formed are {Fez&)- assemblies bear ing l i g a t e d C0.l1O The [Fe2S2I2+ core, l i g a t e d by a [Fe2S2(C0)6l2- moiety on each Fe atom i s a l so a fea tu re o f the s t r u c t u r e o f the [Fe6S6(C0)12l2- ion.”’

f e r e n t Fe6 arrangement i s found i n the [Fe6S6Cle{Mo(C0)3}2]I+- anion. ‘12 bonding i n the [Fe2E2(C0)6I2- an ion (E = S o r Se) has been the sub jec t o f a t h e o r e t i c a l i nves t i ga t i on . Fur ther advances i n promoting c o n t r o l l e d c l u s t e r condensation and a d d i t i o n reac t i ons o f sulphido-carbonyl d e r i v a t i v e s have been

r e p ~ r t e d , ” ~ and the d i f f e r e n c e i n r e a c t i v i t y between f i r s t and t h i r d row t r a n s i t i o n metal c l u s t e r s has been demonstrated i n a study on the reac t i ons of [ M ~ ( C O ) ~ ( U ~ - S ) ~ ] (M = Fe o r 0s) w i t h Me2NH. f o r the Fe complex, amine a d d i t i o n and format ion o f a C,O-bonded b r i d g i n g

N,N-dimethylcarbamoyl l i g a n d occurs f o r t he 0s analogue. Several t r i n u c l e a r metal sulphido-carbonyl d e r i v a t i v e s have been i s o l a t e d and cha rac te r i sed f o r t h e

f i r s t time, i n c l u d i n g [ R u ~ ( CO) 10 ( c(3-S)11 l6 and thz [ I r g ( CO)6( ~3-S)2]- anion. l 7

The l a t t e r conta ins very l ong Ir-Ir bonds (3.086 A), suggesting very weak, i f any, metal-metal i n te rac t i ons . Fur ther s tud ies on metal carbonyl d e r i v a t i v e s con ta in ing Se’l8-l2O o r Te120 have been described. These inc lude d e t a i l s of

the second c r y s t a l s t r u c t u r e determinat ion of t he [ W ~ S ~ I + ( C O ) ~ O ] ~ + ion,118 and

the f i r s t on the [FeWSe2(CO)e12+ c a t i ~ n . ” ~

spectroscopy o f metal carbonyls con ta in ing s i n g l e heteroatoms w i t h i n the metal c l u s t e r s have a l so appeared. 121

A completely d i f - The

Whereas CO s u b s t i t u t i o n occurs

Papers devoted t o the v i b r a t i o n a l

5 Metal Carbonyl Hydrides

The r e l a t i o n s h i p between metal carbonyl hydr ides and d i hydrogen complexes o f metal carbonyl d e r i v a t i v e s has been f u r t h e r explored. 122-127 The i n t e r - ac t i ons o f d6 ML5 fragments w i t h H2 have been s tud ied by EHMO methods,lZ2 and

the s t ruc tu res and some reac t i ons o f n2-H2 complexes o f C r , Mo, W, Fe and Co

carbonyl d e r i v a t i v e s examined. 123-125 In t ramo lecu la r 1 igand rearrangements i n [M(CO)sH]- anions (M = C r o r Mo) have been inves t i ga ted us ing v a r i a b l e tempera- t u r e 1 3 C n.m.r. A t w i s t mechanism t h a t prov ides a pathway f o r i n t ramo lecu la r

ax ia l -equa to r ia l CO exchange i s favoured. 126 anions i n the reduc t i on o f aldehydes and ketones by hydrogen has a l so rece ived a t t e n t i o n . 127 A Mn-H bond d is tance o f 1.65 * 0.05 A has been determined from

n.m.r. r e l a x a t i o n t ime stud ies i n s o l u t i o n , l Z 8 and the p o t e n t i a l o f t h i s method

f o r molecular s t r u c t u r e s tud ies on l ess robust species was noted. l y s i s of [FeH(CO),]- and the photochemical a c t i v a t i o n of H2 by Fe(C0)S have been studied, lZ9, 1 3 0 and the spectroscopic, k i n e t i c and thermodynamic a c i d i t y

of t r a n s i t i o n metal hydr ido carbonyls determined.131 De ta i l ed v i b r a t i o n a l sPectroscoPic s tud ies on [M3(C0)12(~-H)3] (M = Mn o r Re) have been pub-

The c a t a l y t i c r o l e o f these

0

The photo-


l i ~ h e d , ' ~ ~ - ' ~ ' + and f o u r separate f l u x i o n a l processes have been detected us ing n.m.r. methods f o r MeCN so lu t i ons o f the [Re3H3(CO)lo]2- anion. an example o f t he r o t a t i o n o f an RezRe fragment on R ~ H ( C O ) I + . ~ ~ ~

stud ies on the [Re3(CO)lo(pH),]' anion,136 and reac t i ons o f t h i s species w i t h Me3N0137 and w i t h p h o ~ p h i n e s l ~ ~ have been reported. Reaction between [Re3H3- (CO)lo(NCMe)] and [ReH2(CO)'+]' a f f o r d s the novel [Re4(~-H)5(CO)14]- an ion which

contains a b u t t e r f l y m e t a l l i c ske leton w i thou t b r i d g i n g l i gands between the wing tip^.^^^ An x-ray examination o f PPN[OSL+H~(CO)~~] has been c a r r i e d

and the synthes is , s t r u c t u r e and spect roscopic p roper t i es of [ R u ~ R ~ ~ H ~ ( C O ) 121

r e ~ 0 r t e d . l ~ ~ A general rou te f o r the preparat ion of t e t ranuc lea r c l u s t e r s con-

t a i n i n g Ru3 and Os3 t r i a n g l e s has been published, i n which [M3(CO)lo(NCMe)2] (M = Ru o r 0s) i s reacted w i t h a metal carbonylate anion.

[ R u ~ O S H ~ ( C O ) ~ ~ ] and [Os3RuH(CO)3]- are formed on p r o t o n a t i o n o f the products.142

Metal l o - s e l e c t i v e reac t i ons o f [Co3RuH( CO)12] have been observed i n which CO bonded t o Ru i s s u b s t i t u t e d by amines, whereas phosphine s u b s t i t u t i o n occurs exc lus i ve l y a t C O . ' ~ ~

have a l so been studied.14'+ achieve the stepwise bu i l d -up o f osmium carbonyl c l u s t e r s have been pub- l i ~ h e d . ' ~ ~ ~ " + ~

e lec t ron c l u s t e r [ O S ~ H ~ ( C O ) ~ ~ ] as one w i t h Me3NO i n the presence o f [OsH2(C0)4] y i e l d s the new heptanuclear c l u s t e r s [ O S ~ H ~ ( C O ) ~ ] (z = 22, 2 1 o r 20), whose metal geometriesare d e ~ c r i b e d . ' " ~ The bimetal 1 i c carbonyl c l u s t e r s having the general formula [ N i gPt3( C0)21H~+-n]"-

(n = 4, 3 o r 2 ) r e s u l t from the r e a c t i o n of [Ni6(CO)1,]2' w i t h K2PtC14. The [NigPt3(C0)21H]3- and [Ni12(C0)21Hl3- anions are i s o s t r u c t u r a l , w i t h the P t

atoms i n the former occupying the i n n e r t r i a n g l e o f t he c e n t r a l N i 3 P t 3 p lana r t r i angu la ted array.147 i t i o n metal compounds i s w e l l known, bu t i t has been shown t h a t i n some cases

ab initio MO c a l c u l a t i o n s are able t o l oca te the H atom by d i r e c t c a l c u l a t i o n o f t o t a l energy f o r var ious H atom 1 0 c a t i o n s . l ~ ~

6 Metal Carbonyl Halides

These inc lude

Fur ther n.m.r.

The hydr ido species

Ligand s u b s t i t u t i o n k i n e t i c s of the [Ru3H(CO)ll]' anion

Fur ther examples o f t he use o f [OsH2(CO)'+] t o

Reaction o f [ O S ~ ( C O ) ~ S ( N C M ~ ) ] w i t h O S ~ ( C O ) ~ ~ y i e l d s the 88- whereas t reatment of O S ~ ( C O ) ~ ~

F i n a l l y , the d i f f i c u l t y o f l o c a t i n g H atoms i n t rans -

Oxidat ion w i t h I 2 o f [Mo(v6-arene) (CO),] y i e l d s [Mo(n6-arene)(CO)31]- [M0215(C0)6], which conta ins a novel an ion o f approximately C z v symmetry. Each Mo atom i n the anion i s 7-co-ordinate, be ing bonded t o th ree b r i d g i n g and one te rm ina l I atom, and th ree te rm ina l CO l igands. The analogous tungsten

anion was a l s o prepared.149 and mer-[Ru(C0)31,]- have been examined. atmosphere, t he d imer ic d ian ion [Ru,(CO),I~]~- o f S2 symmetry i s formed.150 High y i e l d synthesesof [ O S ~ ( C O ) ~ ( U - I ) ~ ] and [os2(c0)812] have been repor ted, lS1

and a f a c i l e synthes is o f Mo:Mo con ta in ing species described s t a r t i n g from

The synthes is and r e a c t i v i t i e s o f s a l t s o f fac- On heat ing the fac-isomer i n an argon

[Mop ( co) 8 141. 52

Metal Carbonyls 15s

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138 139

140 141

H. Lang, G. Hut tner , B. Sigwarth, I. J i b r i l , L. Zsolnai and 0. Orama, J. Organomet. Chem., 1986, 304, 137; A. Gourdon and Y. Jeannin, - i b i d , 1986, 304, C1. F.T. Al-Ani , D.L. Hughes and C.J. P i cke t t , x, 1986, 307, C31. G.L. L i l l y , E. Sinn and B.A. A v e r i l l , Inorg. Chem., 1986, 25, 1073. M.G. Kanatz id is and D. Coucouvanis, J. Am. Chem. SOC., 1986, 108, 337. T.D. Wea the r i l l , T.B. Rauchfuss and R.A. Scot t , Inorg. Chem., 1986, 3, 1466. R.D. Adam and S. Wang, Inorg. Chem., 1986, 5, 2534; R.D. Adams, J.T. Horva'th and S. Wang, u, 1986, 5, 1617; R.D. Adams, J.E. Babin and H.S. K im, u, 1986, 25, 1122. R.D. Adams and J.E. Babin, u, 1986, 3, 3418. R.D. Adams, J.E. Babin and M. Tasi, E, 1986, 4514. R.D. Pergola, L. Gar lasche l l i , S. Martinengo, F. Demartin, M. Manassero and M. Sansoni, J. Chem. S O C . , Dal ton Trans., 1986, 2463. M.J. C o l l i n s , R.J. G i l l e s p i e , J.W. K o l i s and J.F. Sawyer, Inorg. Chem., 1986, 25, 2057. D.J. Jones, T. Makani and J. R6ziere, J. Chem. SOC., Chem. Commun., 1986, 1275. W. Beck, W. Sacher and U. Nagel, Angew. Chem. I n t . Ed. Engl., 1986, - 25, 270. C.E. Anson, J. P. A t ta rd , B.F.G. Johnson, J. Lewis, J.M. Mace and D.B. Powell, J. Chem. SOC., Chem. Commun., 1986, 1715; C.E. Anson, J.P. A t ta rd , B.F.G. Johnson, J. Lewis, J.M. Mace and D.B. Powell, - i b i d , 1986, 1715; 1986, 108, 2894. Y. J e a C O . Eisenste in , F. Volatran, B. Maouche and F. Sefta, J. Am. Chem. SOC., 1986, 108, 6587. R.K. Upmacis, M. P o l i a k o f f and J.J. Turner! u, 1986, 108, 3645. H.J. Wasserman, G.J. Kubas and R.R. Ryan, w, 1986, 108, 2294. G.E. Gadd, R.K. Upmacis, M. P o l i a k o f f and J.J. Turner, u, 1986, - 108, 2547. D.J. Darensbourg, M.Y. Darensbourg, R.L. Gray, D. Simmons and L.W. Arndt, Inorg. Chem., 1986, 25, 880. P.A. Tooley, C. Oval les, S.C. Kao, D.J. Darensbourg and M.Y. Darensbourg, J. Am. Chem. SOC., 1986, 108, 5465. T.C. Fa r ra r and G.R. Qu in t i ng , J. Phys. Chem., 1986, 90, 2834. C. Pac, K. M.iyake, T. Matsuo, S. Yanagida and H. Sakurai, J. Chem. SOC., Chem. Commun., 1986, 1115. P.J. Krus ic , D.J. Jones and D.C. ROC, Orqanometal l ics, 1986, 5 , 456. J.F. Nixon, E.A. Seddon, R.J. Su f fo l k , M.J. Taylor, J.C. Green and R.J. Clark, J. Chem. SOC., Dal ton Trans., 1986, 765; E.J. Moore, J.M. S u l l i v a n and J.R. Norton, J. Am. Chem. SOC., 1986, 108, 2257. M.K. Howard, P. Skinner, R.K. Bhardwaj, LA.. Jayasooriya, D.B. Powell and N. Sheppard, Inorg. Chem., 1986, 25, 2846. U.A. Jayasooriya and P. Skinner, u, 1986, 25, 2850. U.A. Jayasooriya, S.J. Stotesbury, R. Gr in ter7D.B. Powell and N. Sheppard, fi, 1986, 2, 2853. T. B e r i n g h e l l i , G. D'Alphonso, H. M o l i n a r i , B.E. Mann, B.T. Pickup and C.M. Spencer, J. Chem. SOC., Chem. Commun., 1986, 796. T. B e r i n g h e l l i , G. D'Alfonso and H. Mo l i na r i , Magn. Res. i n Chem., 1986, - 24, 175. T. B e r i n g h e l l i , G. D'Alfonso, M. Freni , G. Cianni and H. Mo l i na r i , J. Organomet. Chem., 1986, 311, 177. T. B e r i n g h e l l i , G. C ian i , G. D'Alfonso and M. Freni , u, 1986, 311, C51. T. B e r i n g h e l l i , G. C ian i , G. D'Alfonso, V.D. Malde, A. S i r o n i and- M. Freni, J. Chem. Soc., Dal ton Trans., 1986, 1051. M. McPar t l i n and W.J.H. Nelson, 1986, 1557. I. Pursiainen, T.A. Pakkanen, B.T. Heaton, C. Seregni and R.G. Goodfellow, - i b i d , 1986, 681.

U.A. Jayasoor i ja and C.E. Anson, J. Am. Chem. SOC.,

Metal Carbonyls 159

142 143

144 145

146

147

148 149

150 151

152

G.A. Foulds, B.F.G. Johnson, J. Lewis and R.M. S o r r e l l , m, 1986, 2515. M. H ida i , H. Matsuzaka, Y . Koyasu and Y . Uchida, J. Chem. SOC., Chem. Comnun., 1986, 1451. D.J. Taube and P.C. Ford, Organometal l ics, 1986, 5 , 99. B.F.G. Johnson, R. Khat tor , J. Lewis, M. McPar t l in , J. Mor r i s and G.L. Powell, J. Chem. SOC., Chem. Comnun., 1986, 507. B.F.G. Johnson, J. Lewis, M. McPar t l in , J. Morr is , G.L. Powell, P.R. Raithby and M.D. Vargas, w, 1986, 429. A. C e r i o t t i , F. Demartin, G. Longoni, M. Manassero, 6. Piva, G. P i ro , and M. Sansoni, J. Organomet. Chem., 1986, 301, C5. C.F. Halp in and N.B. Ha l l , J. Am. Chem. SOC., 1986, 108, 1695. A. Ba rba t i , F. Calderazzo, R. P o l i and P.F. Zanazzi, J. Chem. SOC. Dal ton Trans., 1986, 2569. J.R. Zoel ler , Inorg. Chem., 1986, 2, 3933. G.L. Geoffroy, S. Rosenberg, A.W. Her l i nge r and A.L. Rheingold, w, 1986, 25, 2916. F.A. Cotton and R. P o l i , J. Am. Chem. SOC., 1986, 108, 5628.


9 Organometallic Compounds containing MetaI-Metal Bonds

BY W. E. LINDSELL

1 Introduction

A number of the published papers from the 20th International Conference on Organometall ic Chemistryla and from the 5th International Conference on the Chemistry and Uses of Molybdenumlb concern metal-metal bonded compounds.

1.1 Reviews. - Accounts of dinuclear compounds cover derivatives with saturated hydrocarbon bridges , d 1 nuc 1 ear meta 1 1 ocenes3 and the chem i stry of the 02n4 triple bond between Mo or W atoms.4 Two new books5 on metal clusters include several chapters on organometallic species, and a general article on molecular clusters is of interest.6 High nuclearity clusters' and clusters with opened transition metal polyhedra8 are surveyed; other aspects of polynuclear compounds reviewed include the bonding of clusters and its relationship to bulk metals' and applications of computer graphics in the study of metal cluster compounds." Species containing main group elements are discussed in an account of complexes with divalent Si, Ge, Sn and Pb as ligands'l and also in the context of multiple bonding between transition and main group elements.12 Personal reviews in the commemorative 300th volume of J. Orgartomet. Chem. by W . A . G . Graham, W.A. Herrmann, J.K. Kochi and K. Vrieze are also of relevance to this chapter.

1.2 Theoretical Studies. - Fenske-Hall molecular orbital calculations are reported for the asymmetric bridging of the methyl group in [Fe2(~-Me)(~-CO)(CO)2Cp2 1: l3 for models of monocarbonyl adducts of M2(0RI6 (M - Mo, U)14 and for binuclear complexes [M2(pL)2Cp21 (L = NO, M = Fe, Co; L = CO, M = Co, Ni)115 occupation of a Co-Co antibonding orbital stabilises [Co2(p-CO)(p-NO)Cp2 I and [CO~(~L-CO)~C~~I- relative to [ C O ~ ( P - C O ) ~ C ~ ~ I . ~ ~ ~ Studies on alkyne bridged species [M2(~-C2R2)(C0)61 (M - Fe,16a Col7) are coupled with UV-PES data for the Fe2 species, as for related flyover bridged Fe2 derivatives,lbb and with the experimentally determined electron deformation density distribution for the Co2 specie~."~ EHMO calculations support a weak donor-acceptor Ni-Th interaction in [Cp2Th(j~-PPh2)2Ni (C0)2 ].I8

The role of d-orbitals in EHMO calculations of transition metal clusters is A general class of N-atom, polar deltahedral clusters with


Organometallic Compoundr containing Metal-Metal Bonh 161

N-skeletal electron pairs is defined.20 Topological models for clusters of Os, Au, Pt and Rh are presented21 and atomic arrangements and electronic requirements of close packed circular and spherical clusters are discussed. 22 A surface force field has been developed for the molecular mechanics simulation of 1 igand structures in carbonyl clusters23 and the importance of deformations of the metal framework is noted in estimating strain energies associated with 1 igand additions to clusters. 24 Polyhedral rearrangements of clusters may involve preferred single edge cleavage mechanisms.25

Electronic structures are calculated for the following cluster systems: [Re3 (p-0 1 (Cp* - n5-C5Me5 1, 26 [HjOS3 (BCO) (CO 19 1 and [H20~3 (CCO) (CO 19 1, 27 [Cp2C03(CO)412-, 28 [Fe5C(CO)151,29 [HFe5N(CO)141,29a arene and phosphine substituted C O ~ carbonyl clusters30 and Pt-Au clusters. 31

1.3 Physical Studies. - 10gAg{lH) INEPT n.m.r. studies of intramolecular core rearrangements are reported for Ag2Ru4 clusters.32 Substitution reactions on RuCo3 clusters have been monitored by 59C0 and 'H n.m.r. spectro~copy.~~ Applications are recorded of 1D heteronuclear NOE difference spectroscopy in assignment of lH and 13C n.m.r. parameters of dinuclear fulvalene complexes.34 13C relaxation studies on [Re3(~-H)4(CO)101- 35 and multinuclear n.m.r. spectra of PdSn36 and MnSn37 complexes are also reported. Non-equivalent gold sites in clusters are distinguished by lg7Au Mossbauer spectra3* and various iron clusters are studied by 57Fe Mossbauer spectros~opy.~~ The radial distribution function method is useful for X-ray determination of distances between metal atoms in powder samples of clusters1 40 both Fe and Se EXAFS establish core structures for [ F ~ ~ E ~ ( c o ) ~ I Z (E - S, Se) and related species.41

Vibrational assignments are made for [Re(CO)lO-n(CNR)nl (5 = 1-4)42 and for [M3(pH)3(CO)12] (M - Mn, Re).43 The metal-nitride stretching vibrations of [M4(p4-N)(p-H)(CO)12] (M - Ru, 0s) are identified44 and trends in v(Au-Au) vibrations of [Au{ (CH2 I2PPh2) I2X2 species are reported.45 Thermochemical measurements give an energy of 69i5.5 kcal/mol for the MorMo bond in [MO~(CO)~C~; Electrochemical studies on various dinuclear and cluster derivatives are presented.47

- -

1.4 Surface Bound SDecles. - Structures [Os3(p-H)(CO)lo(~-O-oxide)l or [Os3(l-OH) (CO)lO(p-O-oxide) I can be fitted to EXAFS data for the adsorbate of [ O S ~ ( C O ) ~ ~ I on alumina surfaces.48 Solid state 31P n.m.r. of several Os3 clusters tethered to si 1 ica by a 1 igand PPh2(CH2 )2Si (OEt 13 (L) include species having spectra consistent with structures [H2Os3 (CO)~OL] and [ O S , ( C O ) ~ ~ L ~ . ~ ~ Soluble models are compared with tethered [Os3(v-H) (CO)lo{~-S(CH2)3- Si (OEt13) Deprotonatlons of hydrido clusters [H40s4(C0)121, [H2FeH3(C0)131 (H - Ru, 0s) or [ H F ~ C O ~ ( C O ) ~ ~ ] on hydroxylated magnesia form the respective


adsorbed anions;51 also, It can be abstracted from [H~OS~(CO)~~II on this surface.51a The generation of [HFe3 (CO)ll]- from Fe3(C0)12 on hydroxylated Y - A ~ ~ o ~ has been studied. 52 EXAFS measurements of ~h~ ( ~ 0 1 ~ 6 supported on y-A1203 show fragmentation reactions with 02 and H2 but cluster regeneration on treatment with CO and H20.53 Mononuclear 0s or Ru complexes on MgO surfaces are converted during catalytic hydrogenation into [ o s ~ ~ c ( c o ) ~ ~ 12- or [ R U ~ C ( C O ) ~ ~ I?- re~pectively.~~ Decompositions of Fe-Ru bimetal 1 ic clusters on interaction with oxide surface have been investigated.55

2 ComDounds with Homonuclear Transition Metal Bonds

2.1 Titanium. - The bonding of titanium clusters with formulae CpiTi4S80L- (cp' = v5-C5H4Me, X = l,2),56a Cp5Ti5S656b and Cp8Ti6Nli (x = 1,3)56c may include an element of direct interaction between Ti atoms.

2.2 Vanadium. - Alkali metal reduction of diindenylvanadium gives paramagnetic d i i ndeny 1 d i vanad i um (1 w i th V-V 2.3 51 b; . 57 D i nucl ear vanad i um complexes with four, electron-deficient alkyl bridges, [Cp2V2(p-C4H8)2] ( c ~ H ~ = 1,4-butanediyl) and [Cp;V2(p-Me)41, are ~haracterised.~~ The crystal structure is reported for [CP~V, (p-se) (p-n-se2 1 (p-se2 I I ; 59 clusters [cp$Vgsg I , [cp5v6 (~3-0 180 1 and [(cp5v6 ( ~ ~ - 0 18) 2(p-0 11 may incorporate some direct V-V bonding.6o

2.3 Chromium, Molvbdenum and Tunasten. - Benzylidene bridged complexes [W2(p-CHC6H4R-p) (cO)10 ] are formed by thermolysis Of [w(cHc6H4R-p)(co)5].61 Properties of phosphinidene, arsinidene and stibinidene bridged species of Cr, Mo and W, including the crystal structure of [ (OC)l~W2(~3-AsPh)W(CO)51 and related iron complexes, are described.62 Ligand exchange on [Mo2 (W-PE~~)~(CO)~] occurs by a dissociative mechanism.63 Both Mo-Mo and C-C bonds are cleaved on photolysis of [Mo2(pBut-IAE) (COI6 I , where But-IAE is bis(1-t-butyl imino-2-t- butylaminoethane) acting as 10-e donor.64 Mo-MO bonded species [ Mo2 (p-dttd ) (CO 1 Idttd = 2,3,8,9-di benzo-1 ,4,7,10-tetrathiadecane (2- 11 contains a new type of tetradentate bridge.65 Triply bonded [Mo2(COI4- {HB(p~)~l~l has MosMo 2.507(1)

The photochemical disproportionation of [MoZ (C0),Cp2 1 with PPh3 and the back reaction have been studied.67 Complexes [M2(p-Q5:n5-C5H4SiMe2C5H4)(CO)6] (M = Mo,W) with a linked cyclopentadienyl bridge and their reactions with P2Me4 are described.68 The structure and reactivity of fulvalene bridged [ M O ~ (p-r-2: n 5 - ~ ~ ~ ~ ~ ) (co)~ I are reported6' and a fulvalene bridged structure occurs in a form of dinuclear molybdocene with methylcyclopentadienyl ligands, [ M O ~ ( ~ ( - ~ ~ : , ~ - C ~ ~ H ~ M ~ ~ ) H ~ C ~ ~ Atulene bridged [Cr2(p-C10H5Me3-4,6,8)(C0)6]

Organometallic Compounds containing Metal-Metal Bonh 163

Mezp\ CHZ /PMez

( 6 )

H H., 1 .

H C F N R

/\CH\ ,Co OC\Fe -\-Fe

OC' \RN h H C f I C02Me

Ph

I64 Organometallic Chemistry

contains a long Cr-Cr bond.71 Dinuclear peralkylcyclopentadienyl polyhydrido complexes [ w ~ H ~ c ~ ; I and [W2 (p-115: n5-Et4C5CH2CH2C5Et4 )H8 1 are characterised, 72 as is [W2(p-H)2H2(N0)2Cp2] which has been subjected to detailed ‘H n.m.r. ana 1 ys i s .73

Photolysis of [W(C(tol-p)} (CO)2Cpl in the presence of CO yields [W2{p-{C (tol-p } ,COI (CO )4Cp2 I . 74 Full detai 1 s are pub1 ished for p-a1 lyl idene complex [Mo2 ( p o : n3-CHCHCMe2 (C0),Cp2 I , prepared from 3,3-dimethylcyclo- propene: this complex undergoes oxidation to a mixed-valence oxide, rearranges on thermolysis and reacts with dienes or alkynes to give various products with organic bridging l i g a n d ~ . ~ ~ A flyover bridge formed from three alkynes is present in [ M ~ ~ ( p - o , ~ ~ : n ~ , U - C ~ M e ~ ) ( C O ) ~ ( n ~ - i n d e n y l 121 which adds two co ligands with Mo-Mo bond lengthening.76 Alkynyl bridged anions [M2(p-CXR)(C0)4Cp2]- and related species are reported;77 these can be protonated or methylated and when R = CMe=CH2 protonatlon gives complexes (2) and (31, (M = Mo, W). Initial CO substitution by PPh3 on [Mo~(~-C~H~)(CO)~C~~ 1 is followed by isomerisation to (4).78 The diadduct of [MO~(CO)~C~;] with CF3NC isomerises with C-C bond formation and Mo-Mo bond ~leavage.~’ Addition products of diazoalkanesaoa and of carbodi imidesaob with [Mo~(CO)~CP~I are described.

Complex [Mo2 (K-PAr) (C0),Cp2 1 (Ar = 2,4, 6-Bu5C6H2) is structural ly characteri sed’l as, a1 so, is [Cp;Mo2 (CO l 2 (~(3-p~ l 2 {Cr (CO 15) 2 I which i s related to [Mo2(p-n2-E2),(C0),Cp; I (E = P, As) and [ M ~ ~ ( p - n ~ - A s ~ ) ( C o ) ~ C p ~ l . ~ ~ Sulphur complex [Cr2(pS)2(~-S2)Cp2 Ia3 and selenium complex [Cp2(0C)4Cr2(p3-Se)Cr- (CO)2Cp]- 84 are formed from [{CpCr(C0)2}2El where E = S or Se, respectively. Methylation of [Mo2 (c(-SI2 (p-S2)Cp; I produces two isomers of [Mo2 (SMe)2S2Cp; Ia5 and dinuclear tungsten complexes [W2(p-S)2EE’Cp2 I, with E/E’ variously NSiMe3, S or 0, are obtained from reactions of S(NSiMe3)2.86 Other reported dinuclear sulphur bridged species include [Mo2(p-SC(CH2)3Sl (CO),Cpi [Mo2(b-SBut)2- (CO)4Cp2 12+ and [M~~(p-sMe)~(Co)~Cp~l~ 88 and products from reactions at the sulphur 1 igands of [Mo2 (k-S2CH2 1 (b-S)2Cp2 I.”

[Mo2(BnzI6] has been structurally characterised:” related alkyl alkoxides [Mo2R(OR’ 151 and [W2R2(0R’ 14Ig1 and the tetracarboxylate [Mo~(~OAC),(CH~BU~)~ Ig2 are also reported. Addition of 1,3-diaryltriazene to anti and gauche [W2Et2(NMe2I4 I gives three isomeric forms of [W2Et2(NMe2)2(ArN3Ar)2].g3 Combined CO and pyridine addition to [W2C12(NMe2)4] yields [W2C12(NMe2)4(py)2COl:g4 this and related species exhibit low terminal v(C0) vibrations, 1700-1750~m-~. Several alkyne derivatives [ W , ( ~ ( - C , R , ) C ~ ~ ( N M ~ ~ ~ ~ - ~ L ~ I ( L = py,95 PRJ 96) are characterised and, although some possess pseudo-tetrahedral W2(p-C2) cores, when = 4, R = Me, L = py the alkyne is twisted relative to the W-W axis with incipient metallocyclobutadiene character which is analysed theoretical thermal rearrangement of the derivative with 2 = 3, R = H, L = PR3 yields [W2(p-C2H3)(p-CH2NMe)(p-NMe2)C13-

The homoleptic benzyl

Organometallic Compounds containing Metal-Metal Bonds 165

(NMe2)(PR3)2].96 Evidence is presented for equilibria between N-alkyne species [W2(p-C2R2) (OR)6(py)nl and mononuclear alkyl idyne or p3-alkylidyne trinuclear complexes.97 Competition between sclssion of 3-hexyne into alkylidyne ligands and coupling to form j~-a,a:n~-C~Et~ ligand is observed on its reaction with [W2 (OPri 16 (HNMe2I2 related coup1 ing of 2-butyne on [Mo2 (p-NCNEt2) (ONpI6 1 gives [Mo2 (w-C4Me4 (~-0Np 1 (ONp l 5 (NCNEt2 1 I (Np = CH2But 1 which rearranges at 60 into [Mo2{p-C4Me3CH2C (NHINEt2) (ONp 16 1 ."

Structurally characterised trinuclear complexes include opened triangular species [ M O ~ { N ~ - O , O : ~ ~ - C ~ ( C F ~ ) ~ ) (@3-O)(~-C1 )Cp3 ]loo and closed triangular [Mo3(p-n4-CCHCMeCH) (CO)4Cp31 .75a L-Ray structures of cubane-1 ike sulphides [C~,(N~-S)~(~~-L)~CP~ I (L = C0,l0la Sl0lb) are reported. Derivatives [Mo6(p3-Cl )8R4C14-x(PBu3)2], including the structurally characterised all-tram species with x = 2, R' = Et, are formed by alkylation with AlRj of the parent halide (x = 0).'O2

2.4 Manaanese and Rhenium. - Tetraethyldiphosphite (tedip) bridged species [Mn2(~-tedip)x(CO)10-2x] (x = 1,2) arise from substitution of [Mn2(CO)lo].103 Both mer, fac and mer, mer [Mn2(~-dmpm)2(C0)61 {dmpm = bis(dimethy1phosphino)- methane) can be thermally oxidised to radical cations but only the former is a strong photoreductant.lo4 [Mn2(C0)6(depe)21 (depe = bis(diethy1phosphino)- ethane) in solution is in equilibrium with the paramagnetic monomer [Mn(C0I3- depe]lo5 and kinetic studies are reported on transient radicals formed by homolytic Re-Re cleavage, using laser flash photolysis, on compounds of the type [ R ~ ~ ( c o ) ~ L ~ I and [Re2(p-LeL) (co)8].106 The mechanism is investigated for P-0 bond cleavage in chelating 2-pyridyldimethylphosphinite on rearrangement to [ReM(p-OC,H4N)(~-PMe2)(CO)8] (M - Re, Mn) with Re-M bond scission.107 Complexes of type [MnZ (p-~) (w-PR2) (co)&$x] are structural ~y c h a r a c t e r i ~ e d . ~ ~ ~ * ~ ~ ~

The 5-ray determlned structure of [Mn2 (N-CF~ )2 (CO)8 1 is reported. Photoreactions of [Re2 (CO)lo] with ethylene, styrene or isoprene give various di- and trinuclear complexes including structurally characterised [Re3(p-o:n2-C5H7) (CO)13].111 A1 lene and [Mn2(CO)101 form three dinuclear species including [Mn2 (b-n2 : n2-C3H4 1 (CO 18 1 .'I2

Reaction of [Cp'Mn(C0)2(THF) 1 with sulphur ylides (Me2N)RSO(CH2) produces [Mn2(pCH2) (CO)4Cp;]113 or with benzyl azide, [Mn2{w-CON(CH2Ph)N2) (CO)3Cpi],114 an intermediate in the formation of bentyl isocyanate.

EPR studies on mixed-valence dimers [Mn2(p-OR) (CO),Cpi 1 indicate some Mn-Mn intera~ti0n.l~~ Chalcogen bridged species [Re2(p-E)(C0)4Cp;l (E = S, Se, Te) are characterised, and the cation [Mn2(p-TePh) (CO)4Cp2 1' possesses a long Mn-Mn bond (3.010(7)6).117 Protonation at N-0 ligands of [Re(1~-0)~0~Cp;] precedes cleavage by hydrogen halidesllda and the dimer 1s also cleaved by Ph2C=C-0 or by PhNCO.llBb The crystal structure of complex [Re2(w-0I2O2R4 I


( R = CH2CMe2Ph) is rep~rted.'~' Cocondensation of Re atoms with alkylbenzenes is a synthetic route to

p-alkylidene compounds [Re2(p-H)2(p-L)(v6-arene)2 1 with L = CHAr, CMePh or CHCH2Ph;12' cocondensation of Re atoms with benzene and trimethylphosphine forms

Triply bonded [Re2X4(dppm)2] forms A-frame-1 ike monoadducts with isocyanides122a or with C0122b and also mixed carbonyl-isocyanide diadducts;122b ionic species with two or three isocyanide ligands are also formed and a p-iminyl species [Re2 (p-C-NHBut) (p-Cl) (p-dpp~n)~Cl~ (CNBut) I? 123

[Re3(p-H)3(CO)lo]2- exhibits four separate fluxional processes including rotation of an ReERe fragment on ReH(C0)4.124 Substitution reactions on [Re3(p-H)4(CO)10 1- produce complexes of formulae [Re3(~-H)4(C0)9L1-, [ Re3 (p-H l 2 (CO )loL2 1- and, from Me3N0, [Re3 (p-H l3 (CO l 9 (p-0 * * * H* * * NMe3 IT 125 The crystal structure of [Re4(p-H)5(CO)141- is reported.'26

[Re2 (PMe3 14 (V6-CgHg )2 1 .I2'

2.5 Iron. - A mild phase transfer synthesis of [Fe2(p-CH2)(C0)81 is reported'27a and this complex is cleaved by insertion of C0.127b Complex [Fe2{p-CPhC(Ph)H) (~-x)(co)~Iz (X = CO, z = -1) forms the neutral chloro-bridged species (X = C1, z = 0) on reaction with Me30SbC16128a but reacts with other electrophi les giving "[Fe2(p-PhCCPh)(CO)6]," actually containing a ferraindene system.128b Fulvene complexes [M2(p-v5:v1-C5H4CPh2) (CO)gL] (M = Fe, Ru) and related 1,2-benzofulvene species are characterised.12'

Time resolved i.r. spectroscopy is useful in the kinetic monitoring of intermediates, including [Fe2(p-C0l3Cp2I and ~is-[Fe~(CO)~Cp;l, produced on photolysis of [Fe2(CO)4L2] (L = Cp or CP").~~' Crystal structure and solution dynamics of [Fe2(p-CNR)2(CNR)2Cp21 (R = C6H3Me2-2, 6)131a and reactions (R = Me)131b with acids and alkyl iodides are reported. The electronic structure of [Fe2(p-CH2) (p-CO)(CO),Cp21 is compared with that of related species132a and the cislirans isomerisation of the complex has been investigated.132b Reactions of (Fe2(w-CH2)(N0)2Cp21 with trityl cation give p-methyl idyne and p-vinyl derivative^.'^^ Cyclopropyl idene complexes [ F e 2 ( ~ - m H 2 ) (p-CO) (C0l2Cp2 I, structurally characterised for R = Me,134a rearrange thermally or photochemically to p-alkene complexes or, on protonation/deprotonation, to p-alkenyl idene complexes.134b Electrophi 1 ic addition of p-methyl idyne ligand of [Fe2(p-CH)(p-CO) (C0)2Cp2lt to several terminal alkenes forms p-alkyl idyne cations135a but some sterical ly hindered alkenes form 1-alkenyl complexes;135b products from reactions with activated alkenes are also described.136 [Fe2(p-C=CH2) (p-CO)(CO)2Cp2] combines with [Fe2(p-CCH=CHOEt) (p-CO) (CO)2Cp2]t giving tetranuclear [ (Fe2(p-CO)2(CO)2Cp2)2- (p-C5H3)]t 137 and reacts with HCrCCN to form a bridging 4-cyanobuta-l,3- dienylidene 1igan~i.l~~


Radical species [Fe2 (p-CO) (p-CSMe) (CO)2Cp2 I is prepared by l-e reduction of the corresponding cation.13' C- and S- bonded p-C(SR12 groups are present in [Cp(OC)Fe(p-RSCSR)(p-CO)Fe(CO) (NO) I, and in related heteronuclear FeCo and RuCo comp 1 exes. 140

l-Diethylaminopropyne and [Fe2(C0)9 1 or [Fe3 (COI12 1 produce four structurally characterised di- or tri-nuclear complexes, including [Fe2(p- CMeCNEt2)(C0)6] and species with coupled alkyne bri~3ges.l~' Novel C-C and C-N coup1 ing occurs between [Fe2(p-RNCHCHNR) (CO)6 1 and methyl propynoate to form new bridging ligands, as in (5).142

Selective backside attack by nucleophilic anions on [Fe,{p-(PPh,)C,H,-1,2)- (co)6] gives a single diastereomeric anion which subsequently equilibrates with another is01ner.l~~ Anion [Fe2(p-CO) (p-PPh2) (C0)5(PPh2H) I- gives two new products on reaction with ICH2CN, [Fe2(p-L) (p-PPh2)(COl61 (1 = n2-(C,P)-CH(CN)PPh2 or s 2 - ( P , P ' )-Ph2PC(CN)PPh2} .144 Thermal cleavage of a P-C bond in co-ordinated p-R2PCH2PR2 gives products with p-R2PCH2 and p-PR2 ligands, e,g. (6).145 Tetrahedrane molecule [Fe2(p-P2Bu$)(C0)61 and octabisvalene shaped [(Fe2(CO)612(p-P2R2 12 1 are structurally characterised,146 as are triphosphine species of the type [Fe2(p-P3R3)(C0)6] (R - NPrq, alkyl/aryl

The p-CO ligand of [Fe2(p-CO)(p-SR')(C0)6]- is alkylated by RHgX (R = alkyl, aryl) but is displaced by a p-R group on reaction with RHgX (R = vinyl, alkynyl).148 [Fe2(C0)9] reacts with metallodithioester [FpC(S)SFp] to give [ {Cp2 (CO l2 (p-CO)Fe2} (p-SCS )Fe2 (C0l6 ]I4' and with organic di thioesters giving [Fe2{p-CR(SR' )S} (CO)5L] (L = CO) for which substituted products (L = P(OMeI3, CNR , etc. ) are described, Boron d i th i o 1 ato comp 1 exes of types [Fe2(p-S2BX)(Co),] and [F~~(~-s~B~x~)(co),I are reported.151 A range of complexes with bidentate bridging sulphur ligands of general formula [Fe,(p-~S)(CO),] have been in~estigated'~~ and p-disulphur di iron entities act as sulphur ligands to other metal centres in several systems.153

[Fe3(p3-RC2R) (CO)g], with perpendicularly oriented alkyne, undergoes two 1- e reduction steps to form a dianion in which the alkyne adopts a parallel 0rientati0n.l~~ Alkynes react with [HFe3(COIl1 1- to yield bi- and tri-nuclear products, including [Fe3 (p3-CCH2R) (CO),o 1- which is converted on loss of CO into [HFe3(p3-C-CHR)(CO)9]- and, when R = Ph or Pr, loss of H2 produces [Fe3(p3-C=CR) (C0lg 17 155 mechanistic studies of related proton induced hydrogenation/dehydrogenation of p3-vinylidene/p3-ethylidyne clusters indicate an unsaturated inter~nediate.'~~ Coup1 ing of N with p3-ethylidyne on triiron clusters forms [Fe3(NCMe) (C0lg whereas C-C and C-N coupling of Ph2CN2 with a CO and two p3-alkyl idyne 1 igands of [Fe3 (p3-CMe 1 (p3-COEt 1 (C0lg I produces [Fe2 { p-Ph2CNNC (0 ICMeCOEt) (CO l6 1. 158

Cluster ferraboranes [Fe3(p-H)(p3-BHnR)(CO)glZ (n - 2, z = -1; 11 - 3 ,

-

including P-bonded adducts with Cr(C0)5.147b

-

168 Organome t a l k Chemistry

z - 0) are characterised and their substitution or fragmentation with Lewis bases reported .I5'

Alkynes react photochemically with clusters [Fe3(p3-PR)(CO)101 initially forming a P-C bond which may be broken in subsequent skeletal rearrangements;160a under similar conditions alkynes and [Fe3(w3-PRI2 (C0)gI form [ F ~ ~ ( ~ L ~ - R P C R ' - C R ' P R ) ( C O ) ~ ] . ~ ~ ~ ~ The anion [Fe3(u3-PR) (C0)gl2- reacts with CH212 to give phosphaalkene bridged [Fe3 (w3-RP=CH2 1 (C0110 and phosphaalkyne complexes [M3(p3-ButCP)(p-H) (CO)g] (M - Fe, Ru) are reported.162 Radical anions and dianions of [Fe3(p3-PR)2(C0)91 are produced by reduction and the former is implicated in electron transfer catalysis of ligand substitution on this ~1uster.l~~ Phosphorus atoms capping closed triangular tri iron clusters bind additional metal fragments in [IFe3(CO)10) (p4-P)Fe(C0)41- and in species [{Fe3(C0)9) (p4-P)2(MLnl21 (M = Cr, Mo, W, M r 1 1 . l ~ ~ ~

Oxidation of

[Fe3 (p3-S (CO)' ] can yield [Fe3 (p3-S (p3-SO (CO )g 1 reaction with Me2NH forms the simple substitution product [Fe3(p3-S)2(CO),(Me2NH) 1, whereas the related Os3 cluster gives [OS~(M~-S)~(~-M~~NC-O)(~-H)(CO)~I. 167

Tetra-iron boron clusters [Fe4(p4-BH) (p-H)(C0)12-n(PPhMe2)E1- (E = 0,1,2)

are reported.168 Reactions of alkynes with [F~4(p3-CMe)(C0)121- give [Fe4 (p4-n3-CMeCRCR) (p-CO), (C0lg 1; 16' Unsaturated tetranuclear clusters [Fe4(p4-PR)2(p-CO)(CO)10-_nLI!l (1 = 0 ) readily add 2-e ligands (L) and substitution of CO to form fluxional species (n = 1-41 is achieved by a sequence of addition/elimination cycles: terminal alkynes, R'CrCH, react with the parent cluster to produce [Fe4 (p4-PR) (p4-RPCR'CH) (CO)ll] .170 Syntheses and structures of [Fe5C(CO)13(~O) I- and [F~,c(co),~(NO),I~- are re~0rted.l~~

The crystal structure of [Fe3(p3-S)(C0)9 12- is re~0rted.l~~

2 .6 Ruthenium and Osmium. - A full report has appeared of structurally characterised homoleptic complexes [Ru2R6 1 (R = CH2But, CH2SiMe3 1 with R w R u bonds and of related Ru(III), Ru(V) and Os(II1) alkyls, including [Ru~(~-O)~- (CH2SiMe3 16 1 and [0s2 (n3-C3H5 ) 2 (CH2But l 4 I The Ru-Ru bond order of [Ru,(p-PhNpy),(C=CPh) I is 2.5, corresponding to a 0~72~6~(6*?7*)~ ground electronic configuration. 173

12+ and [RU~(CNB~Z)~~]~+ which are derivatives of unknown [RU~(CO)~~I?+ 17* A

diosmacyclobutene ring is present in [OS~ID-C~(COOM~)~) (co)8].175 Unsymmetrical [ R u ~ ( ~ - P ~ ~ P C H - C H P P ~ ~ ) ( C O ) ~ ] has a Ru-Ru interaction which is formally a 2-e donor bond from a square pyramidal Ru to a trigonal pyramidal R~1.l'~ Halogenation reactions of [RU~(~-CO)(~-P"P)~(CO)~] (P P = { (R0)2PJ2NEt) afford several dinuclear products, including [Ru2(p-I) (p-P?')2I(CO)3] and [Ru,(p-PmP)2C12(CO)4

Diazoa 1 kanes, R2CN2, react with a p-n2-C=CPh 1 i gand to form p-n2-a 1 leny 1

- X-Ray crystal structures are reported for cations [Ru~(CO)~(CNBU~

n


derivatives [Ru2(p-n2-R2C=C=CPh)(p-PPh2) (C0l6 Carbonylation of [RU,(~~-C,PP~~)(~-PP~~)(CO)~~I causes cleavage of the P-C2 bond and produces (71.179 High yield syntheses of [os2(~-I)2(co)G] and [os2I2(co)8] are described and the former is converted into structurally characterised [0s2 (p-PPh2)(w-~)(~~)6 1.180 Several carboxylato derivatives are characterised and contain a core unit {Ru~(~-OOCR)~(CO)~) with carbonyl, water or bridging carboxylate 1 igands in axial positions.181

Oxidation of p-vinylidene complex [RU~(~--L)(~-CO)(CO)~C~; I (1 = C-CH2) yields p-ketene derivative {L - p-C(0)CH2} which readily decarbonylates producing the complex with L = p-CH2, whereas reduction forms p-CHMe and a-C2H4 derivatives.182 Detai 1s are given for co-condensation reactions between arenes and 0s atoms with the X-ray crystal structure of a dinuclear product, [0s2 (p-CHC6H3Me2-3, 5 ) (s6-C6H3Me3-1, 3,5 12 1

[Ru2 (p-n2-S2) ( p - n l , nl-Sz) (n5-C5Me4Et)2 I reacts with alkynes to form novel p-1, 2-dithiolene complexes [Ru2(r-n1,s1:s4-S2C~R2) (n5-CgMe4Et)2 The crystal structure of [Ru2(p-SPh)3Cp; 1' is re~0rted.l~~

Complex [ O S ~ B ~ ~ ( C O ) ~ ~ I, with a 1 inear chain structure, undergoes substitution and fragmentation on reaction with phosphines, probably by radical processes.186 Linear [Os3Cl (CO)loCpl is converted thermally into triangulo-cluster [0s3(p-c1 1 ( C O ) ~ C P I . ~ ~ ~

Structures are reported for diphosphine substituted derivatives of [OS,(CO)~~I, h. [O~~(p-dpprn)(CO)~(s'-dppm) and [OS~(CO)~O{ (Ph2P)2- C=CH2) and also for [Os3(CO)lo(CH2=CHOCOMe) 1 with chelating vinylacetate 1 i gand . 189

The ethyl derivative [OS~(~-H)E~(CO)~~ I has an agostic C-H-0s bridging interaction and exhibits a, B and reductive elimination processes.190 Insertion of maleic anhydride into an Os-H bond generates the first structurally characterised cluster with a terminal alkyl 1 igand, [Os3(p-H)- (succinoyl 1 (NCO) (C0lg 1; lgl and [Os3 (p-I)Me(CO)10 1 forms an nl-acetyi cluster on CO insertion.192 Attack at the p-ketene in [Os3(p-CH2CO)(p-I)(CO)101- by nucleophiles R- (R = Me, MeO) also forms 0'-alkyl ligands in [Os3{CHzC(O)R}- (CO)ll 1- whereas attack by electrophi le occurs primarily at the ketene-oxygen to form p-0, s2-vinyl 1 igand.lg3 Carbonylation of n3-ketene species [Ru3(a3-s3-C(0)CH2) (a-CH2) (C0)7(dppm) 1 (8) causes methylene-carbonyl coup1 ing to produce a dinuclear p-v4-oxaal lyl complex [Ru2(r-n4-CH2C(0)CH2)- (CO 1 (dppm 1 1. lg4

Photoisomeri sat ion of a1 kyl idyne [Ru3(: a-C(OMe) 1 (r-H) (CO 110 I to related p-acetyl cluster occurs with methyl migration from 0 to C atom.lg5 Structurally characterised [Os3 (p3-CPh) (p-,-COMe) (C0)g I undergoes alkyl idyne-alkyl idyne coup1 ing on hydrogenation to [OS3(p3-s2-C2(OMe)Ph) ( V - H ) ~ (C0)g ].Ig6 Protonation of the alkylidyne ligand in [M3(p3-CX)(p-H3)(CO)gl (M = Ru, Osr X = alkyl)


generates an agostic M-H-C bridge197a and a related neutral species is implicated in the elimination of CH3X from the clusters (M = Ru: X - Ph, C02Me, OMe) under CO, via sequential formation of three C-H bonds.197b Nucleophi 1 ic additions to [OS~(~-CECH)(~-H)(CO)~] occur predominantly at the a-carbon atom of the pethynyl ligand, although 13-carbon attack may also take place: water attacks U- and 13-sites giving alkyl idyne products [Os3 ( ~ 3 - L ) (p-HI3 (C0)g 1 where L = CH and CCHO, re~pectively.~’~ The para1 lel p3-bonding mode of alkyne in [M3 (p3-n2-RC2R’ 1 (M-H)~ (CO)’ I has been investigated’” and structures have been determined for two isomers of cluster [Ru3(p3-Me2NC3HMe)(p-H) (CO)g], formed from l-dimethylaminob~t-2-yne.~~~

[Ru3 (w-EPhCH2EPh2 1 (r-01-N2Ar) (C0)g I (E = P, As) are characterised2” and cluster [0s3 (p3-ButCH=NNCO) (p-HI2(COl8- (PMe2Ph)l is formed from ButCHN2 by insertion into an Os-H bond and coupling with C0.202 Chiral [Os3(b-H)(pC(0)NHCH2C02Et) (CO)lol has been resolved into enantiomers via conversion into an intermediate diastereomeric substituted der ivat ive . 203

Reduction of the CN bond in substituted benzonitriles on a Ru3 cluster is described204a and the reversibi 1 ity of related imide-amide-nitrene transformations has been demonstrated. 204b p3-Arylnitrene 1 igands in clusters [M3(p3-NAr)2(C0)9] (M = Ru, Fe) can be generated by cleavage of N=N bonds of a~oarenes;~’~ other precursors to nitrene clusters include nitrobenzene in formation of [Ru3(p3-NPh) (Co)7(n6-C6H6) 1206a and nitrosoarenes in formation of [ R U ~ ( ~ ~ - N A ~ ) ~ ( C O ) ~ ~ - ~ ] (11 = 1, 2).206b Dinuclear metallapyrrolidone complexes [ R u ~ ( ~ - P ~ C C R ~ O N P ~ ) ( C O ) ~ ] arise from coupling of CO and alkyne, PhCECR, with p3-nitrene of [Ru3(p3-NPh)(CO)10

thus,

on thermolysis [R~~(p-dppe)~(CO)~I yields [Ru3(p-H) {p3-PPhCHPPh(C6H4 1) (P-dppmI- (CO)71 and [Ru3(p3-PPh) (p3-CHPPh2) (w-dppm) (CO)71?08a reaction of [Ru3(~-dppm)- (CO)lo I with hydrogen gives [Ru3(p-H)(p3-PPhCH2PPh2 (CO)gl and [ R u ~ ( ~ - H ) ~ ( ~ ~ - P P ~ ) ( C O ) ~ ( P M ~ P ~ ~ ) and related derivatives from other Ru3 and Ru4 clusters are also reported.208 Reactions of K[BHBuS] with [Ru3 (p-EPh2CH2- EPPh2 1 (CO I ( E = P, As) afford the dephenylated anions [Ru3 (p3-EPhCH2EPh2 )- (CO)g]- which form mixed clusters with [M(PPh3)It (M = Cu, Ag, Au).~” Phenyl migration from a d i p h e n y l p y r i d y l p h o s p h i n e produces the acyl cluster [Ru3(p3-PPhpy) (p-C(0)Ph)(CO)9].210 Hexanuclear clusters [Os6(p3-PH)- (p-H)2(C0)20(MeCN) I and [ O S ~ ( ~ ~ - P H ) ( ~ - H ) ~ ( ~ - C O ~ M ~ ) ( C O ) ~ ~ ] each comprise two triangular Os3 units linked by a k3-PH group.211

Oxo-bridged cluster [Ru3(p3-O) (p3-CO) (~-dppm)2(C0)51 is reversibly hydrogenated to give [Ru3(~3-O) (P-H)~ (p-dppm)2(CO)~ 1 which forms adducts with a variety of electrophiles.212 A tridentate sulphate 1 igand bridges the triangular framework of [H2Os3(p3-O3SO)(C0)9I

Clusters containing aryldiazo 1 igands

-

Cleavage of phosphine ligands on ruthenium clusters has been studied:

Organometallic Compounds containing MetaCMetal Bonds 171

Phenyl vinyl sulphide forms diastereomers of [Os3 (g-H) (fi-PhSCHMe) (C0)10 1 by insertion into a cluster Os-H bond but undergoes C-S bond scission with [Os3 (co)lo (MeCNI2 I to give [ O S ~ (P-SPh 1 (fi-CHCH2 1 (C0)10 1. 214 Sulphur transfers from ethylene sulphide to a g-CH2 1 igand form [ O S ~ (gn-SCH2 (C0)13-nI (n - 2,3 1, 215 Hydrogenation of [Ruj (g-H (gn-SBut 1 (CO )10+,L2 1 (n = 2,3; L2 - (C0)2, p-dppm) causes C-S bond cleavage and the formation of [Ru3(g3-S)- (g-H)2(C0)7L2]~216 other bidentate ligands, L2, can be introduced by substitution of cluster with L2 = (C012. Photodecarbonylation of cluster [Os3 (P-H 1 (F-SPh 1 (CO ),(C (HINMe2) I yields [ O S ~ (PH 1 (cc-C-NMe2 1 (P-SPh) (CO)8 1 by C-H activation of carbene 1 igand.217 Dimethylamine causes both carbonyl substitution and nucleophilic addition to form p-carbamoyl ligands on [Ru~(JL,-S)~(CO),], one product being [Ru3(fi3-S)2h-Me2NC0)2(NHMe2) (CO)6 The reaction of Me3N0.2H20 with [Os3(~3-S) (C0)10 1 produces [Os3(@3-S) h-H)- (g-OH) (C0)8(NMe3) 1 and six-atom-chain cluster [Os6(g4-S)(g3-S)(g-H)(p-OH)-

[ O S ~ ( C O ) ~ ~ ( P M ~ ~ ) I is an irregular planar cluster which shows remarkable structural non-rigidity, probably involving rearrangement of the metal framework. 220

The intermediate imido cluster formed by protonation of [Ru4 (g4-N) (C0)12 1- is trapped by diphenylacetylene as [Ru4(~4-NH)(g4-n2-C2H2)(CO)11 Acetylene inserts into Ru-P bonds of [Ru4 (r4-PPh 12 (P-CO 1 (CO 110 1 to give [Ru4 ( ~ 4 - n ~ - PPhCHCH)(g4-PPh) (g-CO) (CO)lo].222 Cluster expansion occurs on thermal reactions

phosphinidene species [M30s3(PR) (CO)171 and [M20s3(g4-PR)(CO)l.jl.223 Unsaturated clusters [Ru4 (~4-S)2 (CO)11-n(PMe2Ph)n 1 (IJ = 0-2) have a square

arrangement of metal atoms224a and are structurally related to [Os4(g4-HC2C02Me) (g4-S) (CO)ll ] which readily adds H2 and, subsequently, C0.224b Clusters [oS4(g3-s)(NHMe2)(C0)121 and [ O S ~ ( ~ ~ - S ) ( ~ - H ) ~ ( C O ) ~ ~ ] , formed by addition to [Os4(fi3-S) (C0)121, have butterfly structures.225

Addition of diphosphine to [Os5C(CO)15 1 produces an opened ’wingtip- bridged-butterf iy’ cluster with a monodentate phosphorus 1 igand.226 PPh2H reacts with [Ru5C(C0)51 in two steps to give [Ru5(g5-C)(rr-H)(g-PPh2)(C0)131 in which square pyramidal geometry is retained227 whereas PPh2H adds to [Ru5(g4-v2-C2Ph) (g-PPh2 1 (CO)13 1 without CO loss to produce 78-electron cluster [Ru5(p4-n2-C2Ph) (fi-PPh2)2(~-H)(CO)13 1 with ‘bow-tie’ structure.228 The cluster

characterised and it reacts with CO by insertion into the N-N bond to produce a g4-NC (0 )NCPh2 1 i gand. 229

Reaction of activated raft cluster [ o s ~ ( c o ) ~ ~ ( M ~ c N ) P a with terminal aikyne, RCKH, affords the new organo-cluster [Osg (g3-C=CHPh) (C0)20 1 which subsequently loses Os(COI5 to give [OS~(M~-C=CHP~) (CO)151 with an edge-bridged

(c0)18 1 - 219

of [HOS~(~-PHR)(CO)~O] (R Ph, Cy) with [M3(CO)12I (M OS, Ru) to yield

- -

[Rug ( pq-n2-C2Ph 1 (g4-N2CPh2 1 (g-PPh2 (CO 112 I has a1 SO been Structura 11)’


tetrahedral core. 230b Crystal structures are reported for [Os6 (CO)18-n- (PPh3)n] (n = 1,2) with bicapped tetrahedral geometry231 and for [Os6(p-H)H- (CO)19] with a spiked trigonal bipyramidal structure and a terminal hydride on the pendant OSH(CO)~ group.232 [Osg(p6-P) (C0)18 1- is a phosphorus centred trigonal prismatic cluster233 and distorted trigonal prismatic geometries are displayed by [RU6(p,-PPh)n(p,-PPh)2(co)121 (fi 2 Or 3).234 Isomeric hexanuclear clusters [ O s 6 ( ~ 4 - s ~ ( f i 3 - S ) (P-H)~(C(H)NM~~} (CO)16 1 with opened metal frameworks are formed by pyrolysis of [OS~(I~-H)~(P~-SC~H,)(CO)~(NM~~)

Clusters [OS~(~-H)~ (CO), I (n - 21 or 22 possess novel structures: when n 21, a face capped square pyramid of Os6 atoms is edge-bridged by OS(CO)~~ when n = 22, the core comprises a trigonal bipyramld and a trlangle sharing a common vertex. 236 [RUB (p8-P ( N - C H ~ C ~ H ~ 1 (N-CO 12 (CO 117 I has a phosphorus centred square ant i-pri sm of R U ~ atoms237 and [ ~ u g (~4-s 12 (co)~~(~-cGH~M~ 1 I has an opened structure based on two fused square pyramids of osmium atoms.238

-

2.7 Cobalt. - Crystal structures are reported for the phosphine substituted complex and for the alkynyliron bridged species [Co2(p-PhC=CFp) (CO),].240 Studies of the radical anion [CO~(CO)~{ (PF2l2NMel3I- indicate that the unpaired electron is in an intermetallic a* molecular orbital mainly composed of cobalt orbitals.241 The coupling of alkylidene with CO in complexes [Co2(~-CHR) (p-L) (p-dppm) (Cola 1 to yield ketenes has been studied under CO or S02.242

Photolysis of [M2(p-CO)(C0)2Cp2] (M - Co or Rh) in low temperature hydrocarbon glasses cleanly forms [M2 (p-C0)2Cp2 I .243 Double bonded Co=Co species [ C O ~ { ~ - C ~ ( S ~ M ~ ~ ) ~ } (05-L),] (L - Cp244a or CpR244b) are produced by reaction of the alkyne with respective complex [Co(C2H4)2(n5-L)1: reduction of [Co2C12Cp;] in the presence of RCaCR (R - SiMe3, Ph) is an alternative route to species [Co2(p-C2R2)Cp:] which readily add CO and S02.244b

Oxidative reactions of [Co2(p-PMe2l2Cp21 with CH2X2 (X - Br, I) or halogens form Co(II1) species such as [Co2 (p-PMe2) (p-CH2PMe2 )X2Cp2 I with cleavage of Co-Co bond245a and reactions of [CO~(~-H)(B-PM~~)~CP~ 1' with Lewis bases also open the Co-H-Co system.245b The extent of interaction between d7 Co centres in [CO~(~-X)~C~~] varies from the paramagnetic species with X - halogen, NR2 or OEt to diamagnetic species with X - SMe.246

13C N.m.r. spectra and theoretical studies support a tilted geometry for the ketenylidene fragment in [Co3(p3-CCO) (co)8L] and in related clusters of Fe3 and

Crystal structures are reported for [CO~ (p3-CPh 1 (C0lg ]248 and [ (Co3(p3-CPh) (CO)g)*(p-dppe) and the mechanism of electron-transfer chain catalysed (ETC) substitutlons in these and related clusters are discussed mainly on the basis of electrochemical studies.249 Attempts to resolve chiral [ C O ~ ( ~ ~ - C M ~ ) ( ~ ~ - P ~ ~ P C H ~ P M ~ ~ ) ( C O ) ~ I are described but racemisation of enantiomers

Organometallic Compounds containing Metal-Metal Bonds

occurs under the conditions employed.250 Redox properties of systems with a tricobalt cluster connected to a ferrocenyl group by an amide linkage, as in [FcNHC(O)CCO~(CO)~], show no transmission of electronic effects between C03C and Fc centres.251

Although [Co3(p-CHI2Cp3] is inert to CO at room temperature, the protonated cluster adds CO to give [CO~ (p3-v2-HOC=CH) (p3-CH)Cp3 I: an overall insertion of HCO+ into a metal-alkylidyne NO' similarly inserts into related neutral dialkyl idyne clusters to form the novel clusters [Co3(p3-n2-RC-NO)- (p3-CR' )Cp3]? 253 [Co,{j~~-n~-C~(SiMe~)~)Cp~] and its CO adduct both transform thermal ly into [Co3 (p3-CSiMe3 I2Cp3 I .244a A detai led study of the 46-electron cluster [CO~(~~-CO)~C~; I and a comparative analysis of 48-electron [cO3 (p3-~0)2 (V6-C6H6 l 3 I+ are presented:254 transformation of electron deficient 46-electron C O ~ (p3-CO)q core into normal 48-electron system involves a "net" destabilisation of weak metal-metal interactions but stabilisation of the much stronger metal-carbonyl interactions.254 The [CO~ (~3-C0)2Cp3 1 system is coordinated to Ti via 0-atoms in [CO~ (p3-COTiCp2 )2Cp3 1 .255 Syntheses, structural and electrochemical studies are reported for systems [CO~ (l3-X)-

(fi3-Y)(05-C5H5-xMex)31n (X = CO, NO: Y - NSiMe3, NCONH2, NH).256 Phosphine substituted derivatives of [C04 (COl12 1 reported this year include

polymeric products with dppe, identified spectroscopically, 257 structurally characterised species [ C O ~ ( ~ ~ - H C ( P P ~ ~ ) ~ ) ( C O ) ~ _ , L , I (n = 1,2; L = PMe3; n = 2, L2 = dppm)258 and species [CO,(~-R~PCH~PR~)~(CO)~I for which solution structure and dynamics have been studied.259

Cluster [CO~ (F-CO)~ (COMe) (CO)8 I, which contains a terminal acetyl 1 igand, has been structurally characterised260 and the stereochemical non-rigidity of species [Cod (p-C0)3(C0)6(n6-arene) I (arene = mesitylene, triptycene) has been studied kinetically by using VT 13C n.m.r. spectroscopy.261 Ligand transfer between [Fe21p-C(CF3)C(CF3)SMe}2 (CO12Cp2 1 and CO~(CO)~ affords [C04(/~4-C2-

The cluster unit (CO~(~~-E)(CO)~} (E = P, As) acts as a ligand to transition metal fragments Cr(COI5, W(COI5, Mn(C0)2Cp and c04(cO)11.263 The mechanism of carbonyl substitution by P(OMe13 on [Co4(u4-PPh)2(CO)10 1 changes from associative to dissociative as the extent of substitution increases and electrocatalytic substitution on this system via labile radical anion has also been investigated. 264 Mixed sulphur-phosphinidene tetracobalt clusters [CO~ (b4-S) (p4-PR) (CO)lo I have been ~haracterised.~~~

(cO)8l2- 266a and [CO~(~,-N)(~-CO)~(CO~~I: 26613

173

(CF3 121 (F-co) (COI~CP~ I .z62

Crystal structures are reported for octahedral anions [Cog (4-c) (P-CO)~-

2.8 Rhodium and Iridium. - The sterically crowded complex [Rh2(p(Me2PCH2)2- PMe),(C0),l2' has a structure in which a six co-ordinate Rh atom completes the


four co-ordination of the second Rh atom by a dative Rh-Rh bond.267 The crystal structure of [Ir2(p-H) (p-CO) (p-dppm)2(C0)2 It is reported.268 Bridged 2-pyridyldiphenylphosphine (Ph2Ppy) complex [Rh2(p-CO) (p-Ph2Ppy)2C12 1 reacts with alkynes to give dimetalated alkene derivatives [Rh2(p-a:o-RCaCR' 1- (p-Ph2Ppy)2C12] which form adducts with CO; related diiridium species can be synthesised less easi 1y.269 Structurally characterised [Rh,(j~-0,NO)(p-Ph~Ppy)~Cl~(C0)] contains a bridging nitrato 1 igand.270 The 2,6-bis(diphenylphosphino)pyridine ligands act as tridentate bridges in [Rh2 (p-I) (p-CO) (p-Ph2PpyPPh2 12 1. 271

Iodomethyl iridium(I1) complex [Ir2(p-pz)21(CH21) (COl4 1 transforms intramolecularly into non metal-metal bonded [Ir2(p-CH2) (p-p~)~I~(cO)~ I with a methylene bridge. 272

The X-ray structure of a second crystalline form of metal-metal bonded isomer [Rh2(~-EBu!)2(C0)4] (E = P) is described,273a whereas crystals of the complex with E = As contain planar Rh atoms with no Rh-Rh bond:273b [Rh2(p-H) (p-PBu$) (C0)2(PHBub)2 1 has a long single Rh-Rh bond (2.906 ( 2 Oxidative additions of Me02CC=CC02Me to [M2(fi-PPh2)2(04-cod)2] (M = Rh, Ir) give cis-dimetalated alkene bridged products [M2{b-a;a-C2 (C02Me)2J (p-PPh212- ( ACO~ I. 274

Bis-phosphine adduct [Rh2(0Ac141PPh2 (C6F4Br)12 1 is thermally converted into the ortho-metalated species [Rh2(p-OAc)2{p-P(C6H4)Ph(C6F4Br)) (OAc){PPh2- (C6F4Br)) ].275 Isopropyi groups of two 2,4,6-tri-isopropylbenzenethiol molecules are dehydrogenated on reaction with RhC13 to give co-ordinated a1 kenes in thiolato bridged complex [Rh2 { r-SC6H2Pr& (n2-CMe=CH2 11 2- (SC6H2Prjl2(NCMe) Pyridlne-2-thiol and [Rh2C12(C0)41 afford [Rh2 (p-NC5H4S l 2 (n1-SC5H4NH l 2 (CO l 2 1 with a Rh-Rh bond. 277

Cyclooctatetraene adopts two different bridge-bonding modes in dirhodium complexes [Rh2 (p-17~ : n4-cot 1 (n4-nbd )Cp It and [Rh2 (jt-1,2,6-r): 3-5-n-cot )Cp2 I . 278

[ Ir2 (p-CO (CO 12 ( n5- i ndeny 1 2 I , 279a [ Rh2 (p-CO 1 ( p-n5 :

n5-C5H4C5H4 ) (C0l2 1279b and [Rh2 (p-C0I2 (p-n5: n5-CgMe4CH2C5Me41 1279c are reported. Full details are given for reduction of [Rh2(p-C0)2Cp;lG (5- 0 ) to anions with 12 - 1 and 2 , the latter being structurally characterised as a (KtI2 salt: also described are alkylation procedures to form symmetrical and mixed dialkyls [Rh2RR' (CO)2Cp;] which exhibit cis to t ram isomerisation and undergo 1 i gand- i nduced fragmentations . 280 The cyc 1 opropy 1 ring of a 1 ky 1 i dene bridged complexes [Rh21p-C(R)wH2) (CO12Cp; I opens after photolytic loss of CO to produce [ Rh2 (1-d , n1 : o2-RCCHCH2CH2 (p-CO )Cp; 1. 281

The redox properties of species [Rh2(p-RC2R)(w-CO)Cp21 (R = But, CF3) have been investigated: cations (2t and 1t) and anions (1-1 are observed and the monocation (R = But) is very stable.282 Reactions of [Rh2(p-CF3C2CF3)(p-CO)- Cp2] with alkenes and with alkynes are reported: alkenes react by hydrogen

The comp 1 exes


transfer to give products [Rh2(fi-C(CF3)C(CF3)H) (p-alkenyl )Cp2 1 with crystal structures determined for alkenyi = CH-CHCN and CH-CF2;283a alkynes are incorporated in 1,2-dlmetallacycloheptadione or/and binuclear metalladiene products. 283b Loss of benzene from [Ir2 (p-H 1 ( p - d : v3-CHCHCH2 1 (Ph )Cp; I on addition of 1 igand (L) forms Ir-Ir bonded complexes [Ir2(p-v1:n3-CHCHCH2)LCp;l via an intermediate which is active for C-H oxidative addition.284

Gray selenium cleaves the Rh-Rh bond in [Rh2(p-C0l2Cp;I to form [Rh2(p-Se)- (j~-Se~)Cp;].~*~ There is a short Ir-Ir separation (2.663(1)i) in dihydrido- bridged [Ir2(fi-H)2(~-pz)Cp; I? 286

Full details are presented of thermal or oxidative decompositions of [Rh2 (p-CH2 ),Me2Cp;] to yield methane, propylene, ethylene and some ethane; labelling studies establish that propylene arises from coupling of one methyl and two methylene groups.287 [Rh2(fi-CH2)2X2Cp;1 (X = C1) reacts with RCXMgC1 to give dialkynyl complex (X = C2R) but with BnzMgCl to form structurally characterised [Cp” (Bnz )Rh (p-CH2 I2Rh (v4-C5Me5Bnz) 1. 288

A number of new trinuclear complexes of Rh3 or Ir3 bridged by two triphosphine or diphosphine-arsine ligands (Ph2PCH2I2EPh (E = P; As (dpma)) possess one metal-metal interaction289a and structural ly characterised [Ir3 (p-CO) (M-dpma12 ( ~ ~ 4 1 )C1 (COl2 I+ contains a nearly 1 lnear Ir3 chain connected by two Ir-Ir bonds. 289b

Reversible CO addition to [Rh3 (p-PBu$) (CO 1 1 gives [Rh3 (p-PBuiI3 (p-CO 1- ( C O I 4 1 with expansion of the Rh3 triangular framework.290 Steric effects of bridging ligands control the geometries of planar [Ir4(p-AsBu~)4(fi-C0)2(C0)21, which contains an Ir-Ir double bond, and tetrahedral [Ir4 (p-PCy2 )4(fi-CO)2- (CO)4].291 A new Rh6 geometry, a double edge-bridged tetrahedron, is found in [Rhg (p-H 12 (p-PBU$!q (p-co 12 (co 16 1. 292

Clusters [Ir4(CO)11L] (L = phosphine, arsine, alkene, SO2) and [Ir4(CO)10L2] (L2 = diphosphine, v4-polyalkene) may be synthesised from [Ir4(CO)11Br IT 293

Anions [Ir6(p-CO)4(CO)ll(COOR) I- are formed from attack of [Ir6(C0)16] by NaOR. 294

The anion [Rh12H(p8-N) (fi6-~) (P~-co) ( ~ - c o ) ~ ~ ( c o )~ ~ 13- contains encapsulated nitrogen atoms in trigonal-prismatic and distorted square-anti-prismatic holes.295 Fluxionality of cluster anions [Rh13H,(CO)241(5-”)- (11. - 1-41 and [Rh14H,(C0)25](4-~)- (2 - 0,l) has been studied by V.T. multinuclear n.m.r. spectroscopy. 296

2.9 Nickel. - Nickel ( 0 ) complex [Ni2(fi-CNMe) (p-dppmI2 (CNMe121 can be protonated at the bridging isocyanide ligand.297 The non-1 inear Ni-H-Ni bridge in anion [Ni2(p-H) (C2H4)4]- can be explained by a direct interaction between nickel atoms. 298 Dinuclear complexes [Ni (p-s2: n2-al ka-l,3-diene )Cp2 1 are reported. 299 Complexes [Ni2(~-AsBu~),(PMe3)21 and [Ni2(~-AsBu$)2(CNtol -P)qI have planar


Ni2As2 units with single Ni-Ni bonds.300 [Ni3(p3-CR)Cp3] clusters are formed by exchange between [CO~ (p3-CR) (C0lg 1

and [Ni2(p-CO)2Cp2].301 Non-centred icosahedral Ni12-xAsx (x = 2 or 3) frameworks are present in clusters ~Nilo(AsMe)2(p3-CO)2(p-CO~6(CO~lo12- and [ Ni ( AsPh l 3 (p3-CO l 2 (p-CO l4 (CO l9 ]?- 302 High nucleari ty carbide clusters

(2 = 5 , 6 ) and [Ni35C4(C0)3,l6- have complex core structures which may be related to carbidised metal crystal 1 ites303a and the core of [HNi38c6(p-co)36(co)6]5- is an extended fragment of the c ~ ~ ~ c ~ lattice. 303b

- -

2.10 Palladium and Platinum. - The structure is reported for [Pd2(~-dppm)2(CgClg)2]304a and related [Pd2(~-Ph2PNHpph2)2(cgFg)21 is also described.304b Platinum(1) complexes [Pt2(p-cP)2H(CO) 1' reversibly add one or two CO molecules to form mixed Pt(0)-Pt(I1) complexes with fission of the Pt-Pt bond. 305 The syntheses of a1 lyl bridged complexes [Pd2 (P-C~H~) (K-EY) (PR3 12 1 (E - 0, Y - Ar, Ac; E - S , Se, Y - Ph)306a and of octadienyl-bridged complex [Pd2 (p-OAcI2 (p-1-3-n: 6-8-V-CgH12 ) ]306b are described. Structures are reported for platinum(II1) complex [P~~(P-OAC)~M~~(PY)~ 1 and for four species [Pt,(p-~hp)~Me~(py)~] where Hxhp is 2-hydroxypyridine or substituted derivative and n = 1 or 2 depending on steric effect of the bridging l i g a n d ~ . ~ ~ ~ The l-methyluraci lato (meu 1 complex of platinum (I11 [Pt, (w-meu 12 (meu 1 (NH3 14 13+ is the first example of a nucleobase derivative with a Pt-C bond.308

Linear complexes [ P ~ ~ ( c N C ~ H ~ M ~ ~ - ~ , 618-n(PPh3),~2+ are described with crystal structure for one species ( E = 2 ) beinrrep~rted:~~' reaction of homoleptic species (I! = 0 ) with dppm gives [Pt3(p-dppm)*(CNCgH3Me2-2,6)412t with bent Pt3 chain and A-frame structure.309a Partial and complete substitution of SO2 in [Pt3(p-SO2I3(PR3l3 I by CO is reported.310 Structurally characterised3lla [Pt3(p3-CO) (p-dppmI3l2+ and the palladium analogue react with thiocyanate to form adducts [M3(p3-C0)(p3-SCN) (p-d~pm)~ 1' which rearrange (M = Pd) with loss of CO to [Pd3(p3-S)(p-dppm)3(CN)]+;311b thiols also displace CO from the parent cluster to form p3-sulphur 1 igand~.~ll~ The trinuclear p3-vinyl idene complex with a single Pt-Pt bond, [Pt3(p3-C=CH2)(~-dppm)3Hl~ is formed from acetylene on [Pt3(p3-H) (p-dpp~n)~]' cluster. 312

The cluster [Pt5(p-C0I2 (w-S02)3(CO) (PPh3 l 4 1 has an edge-bridged tetrahedral skeleton313 and high nuclearity [Pd23 (p3-C0)8(p-C0)14 (PEt3 ll0 1 has a centrosymmetric metal polyhedron based on a centred cuboctahedron capped on six square faces and bridged on four edges by Pd atoms.314

2.11 Comer and Gold. - Crystal structures are reported for [Au2{p-(CH2)2- PPh2)2(0COR)2] (R - Ph, Me)315 and species [ I A U ~ ( ~ - ( C H ~ ) ~ P P ~ ~ ) ~ } ~ S ~ I (2 = 8,9l3I6 which incorporate two Au2 complexes in 12 or 13 atom gold-sulphur


rings. Further studies of oxidative addition of organic-halides (CC14, CHBr3, BrCH2CN) to [Au2{ (CH2)PPh2I2], initially forming Au(I1) adducts, are described;317 subsequent reactions with CC14 will yield Au(II1) species.317a Complex [Au2 (p-Ph2PNHPPh2 )C12C6F5)2 ] contains a short Au-Au bond (2.576 (2 111. 318

The distorted octahedral cluster [cU6(~3-0xl )4(p-Br)21 (0x1 = 4,4-dimethyl- 2-oxazoline-4-methylphenyl) has four two-electron three-centre bonded aryl bridges.319 Clusters [Au8(PPh3)7(CNR) 12', [Aug(PPh3)6(CNR)2 13+ and [Aull (PPh3 l7 (CNR I2I 12' have been prepared and the crystal structure of the latter (R = Pri) determined.320

177

3 Compounds with Heteronuclear Transition Metal Bonds.

Tables 1 and 2 list, respectively, the bi- and poly-nuclear complexes containing hetero-transition metal bonds that have been structurally characterised by X-ray diffraction: complexes are entered under the metal of earliest periodic group and arranged in order of (i) increasing group number of other metal(s), (ii) increasing nuclearity (Table 21, and ( i i i ) decreasing number of carbonyl groups. Cp' and to1 are used for n5-C5Me5, v5-C5H4Me and para-to1 y 1 respective 1 y . 3.1 Binuclear ComDlexes. - Heterobinuclear derivatives studied in 1986, which are neither listed in Table 1 nor are simple ligand modified derivatives of these listed complexes, contain bonding interactions between the following pairs of metals: Th and Ni;18 Ti and Au;437 Zr and Ni, Pd, Pt438a or Au;~~' Hf and Rh;324 Cr and Re,369n377 0~4381, or Ir;346 Mo and Re,369 Fe,439 Ru,47a

The abbreviations Cp",

Co,345 Rh,440,441 Ir,346 Ni336 or pt;336 W and Re,369,377 Fe,442 ~0,369 Rh,381 Ni,336 pd,336 pt336,338,381 or Cu;388 Mn and Re,107 Fe,326,443,444 Co,443 Rh,441 pt445~449 or Au;444,446 Fe and 08,438b ~0,140,447 Rh447 or 1r;447 Ru and Col4O or Rh;441 0s and Cu or Au;361 Co and Rh425 or Au;448 Rh and Ir269 or Au;448 Ir and Pt;269 Pd and Pt.47b

Unsupported metal-metal bonds in anions [CrFe(CO)g 12- and [MFeH(C0)8L]- (M = Cr, W ) may be considered as donor-acceptor, Fe-M, interactions;325 similar IrdRh bonds are present in [IrRhCl (C0)2{P(OPri )3}2Cp* Also, [(OC),COR~(CO)(PE~~)~I with Co-Rh (2.676(1)1) is now described in detail and is reversibly, heterolytical ly cleaved by nucleophi les in solution.362 The Mn-Re bond in [MnRe(CO)lO] is shorter than expected.350 Single Rh-M bonded derivatives [ (OEP)RhMLn] are reported for MLn - Mn(C015, Mo(CO)~C~ and Ru (C0)2Cp: 441 Other structurally characterised non-bridged binuclear complexes are [CrFe(C0)5Cp2 1327 and [Cp(OC)3MoPtH(PPh3 12

Metal-gold bonds are present in species [Cp(OC)qMAu(PPh3)1 (M = Ti, Zr)437 and in [Cp(Me3P)2M'Au(PPh3)jf (M' = Co, Rh), prepared from neutral

TABLE

I.

X-RA

Y DETERMINED STRUCTURES OF HETEROBINUCLEAR M

ETAL

-MET

AL BONDED COMPLEXES.

THORIUM

[ThPt(p-PPh2)2(PMe3)CpZf]321

TITANIUM A

ND ZIR

CONI

UM

[TiRh (p-CH,)

( #-CH3) (cod) Cp,]

322

[ ZrR

h (p-OCCH2CH2C5H4) (p-CO) (CO) Cp, ] 323

[ zrRh(p-PPh2) , (q

5-cgri,) cp2

1 324

CHROMIUM A

ND MOL

YBDE

NUM

[CrFeHx(~~)g](2-~- =

0

,1

)~

~~

[CrFe(p-PH(NPri) ) (p-CO) (CO)5Cp]326

[ CrFe (CO) 5Cp2

] 32

7

[CrAu(CO)

(PPh

3) (q5-C5H4CHO) ] 32

8

[MoMn{ p

-O

CC

m,

) ( p-PPh,

) (CO) ,Cp] 329

[MoRe(p-q2-C2Me2) (p-CO) (CO

) (P

Ph3)

Cp]330

[MoRe(p-q2-C2Ph2)

(p-C

O) (C

O) 4( P(0Me) )Cp] 33

0

[MoF

e ( p

-o, q-C (t

ol) =CH2

) (p-CH,)

(CO) 5Cp] 33

1

[MoFe( p-q3-C (to

l) C(0Me) CH)

(CO) 5Cp] 33

1

[MoFe(p-q-SC(to1)

) (CO),CP]~~~

[MoFe(p-q-OC(to1)

) (p-CO) (CO) (NO)Cp2]332

[MOCO(P-~-C~(CF~)~)

(CO),CP]~~~

[MoRh(p-CO) , (CO

) (PP

h3)2

(MeG

a(~z

)3)1

334

[MoPd(p-PCy2) , (C

O) (PPh3

I 336

[MOPd(P-Ph,PPY),

(P-CO) (CO),1337

[MoPtH(CO) (p

Ph3)

,Cp] 338

[MoC

u (p-co)

( PPh

3) (MeG

a (pz) )

] 33

4

-

[MoIr (p-H)

(p-q5:q1-C5H4)H(PMePh2)

,Cp]+

335

TUNG

STEN

[WRe(p-CH(to1)) (CO)g]- 339

[me{ p-m

, (toll

) ( P

- (Me2P) 2cH2

(co) I

339

[WRe(p-OCCH2 Wol) 1 (r-dppm) (CO)61P(OMe) 3

) 13

39

[ WFe( p-PFe2Br (CO) 6

) (CO) 9] 164b

[WFeH(C0)8L)-

(L =

CO, P(OMe)3)325

[WFe(p-q2-Se2) (CO)8]2+ 340

[WFe(p-PH(NPri)

) (jt-CO) (

COi Cpj26

[WFe(p-C(tol)

) (COl5(HB(pz) 3)

1341

[WFe

(p-PPh,) (C

O) 5(HB(pz)

1 134

2

[WFe(p-P(C6H2Bu:)CH=P(C6H2Bu:)

) (CO) ,Cp] 343

IWFe(p-C(tol)

) (P

-CO)

(C-(Me2P) ,CH2) (CO) ,(HB

(P~)

3) 13

41

[ WCo

(p-co) , (

q4-c4Me4) Cp]

345

[WRh(~-co),(Co)

(PP~,),CPI~~~

[WCO( p-C(t01) C(Et) C(Et) C

OH) (CO) 4Cp]

344

[WIr(p-PPh,) 2H(C0)4 (cod) ]346

[ WIr

(p-H) , (p

-q5

: q1-C5H4) H(

PNePh2) ,Cp]+

335

[WPt( p

-q',

q3-CH(tol) ) (p-CO) (C

O) (PEt,) ,Cp]+ 34

7

[ WPt

( P-CO) , (P

Et3 )

, (q -C2H4

) CpI+

[WAu(p-CO) (P-CS) (C

O) (PR3) (

HB(~z)~)] (R =

Me, Ph)3

49

48

MANG

ANES

E

[MnRe(CO)

[ MnC

o ( p

-o , s : q4-C4Ph2Me2

) ( CO) ] 351

[MnC

o (p-PHPh) (CO) 5Cp' ] 263

[MnPt(p-H) (p-CO) (CO) (PEt3),]338

IRON

, RU

THEN

IUM

AND OSM

IUM

[ FeRh (p

-dpp

m) C1 (CO

) 5] 3

52

[FeR

h(p-

q1,q

3-CH

CPhC

O) (CO

) (P

Pri)

Cp]3

53

[FeR

h(p-

q3:q

5-co

t) (CO

)3 (n

bd) ]+ 278

[ FeR

h ( p

-q3

: q4-C7

H7) (C

O) (cod

) 1 354

[FeRh(a-q4:q3-C7H7)

(P-C

O) (CO), (d

ppe)

]354

[FeIr(p-PPh,),Cl

(CO)

3 (c

od) )

]34

6

[FeP

t (a

-dpp

m) (P

-CO

) Br, (C

O) 3] 352

[FeP

t(#-

I) (p-

dppm

)I(C

O)3 ]355

[RuC

o (p-PPh,)

(CO)

(P

Ph3)

] 356

[ RuC

o ( p-PPh,

) (CO)

(d

ppm)

] 357

[RuCo(p-PPh,)

(p-d

ppm)

(Co

) 5~357

[ RuCo (p-PPh,) (C

O) (

P(0M

e) )3 ] 358

[RuR

h(p-

H) (p-

c1) (dppm),(cod)]+

359

[RuRh(fl-H) (p-PhPCH,PPh,)Ph(dppm)

cod]36o

[ OsAg

{ p-C (to

1 ) )

C1, (C

O) ( PPh

3) , ]

61

COBALT

, RH

ODIU

M AND IRI

DIUM

[ CoR

h (CO)

(PEt3), 3 362

[Rh~r~l

(CO) , (p

(opr

i) 3)2~p*~363

[ IrA

u (g-H) , (bi

py) (P

Ph3)

3] 2+

364


[CpM' (PMe3)2] and [PhfPAuCl The formatlon of an Mn-Au bond by elimination of MeH from [(Ph3P)AuMel and [HMII(CO)~I follows a radical-chain mechanism with [MII(CO)~] as chain carrier.446 In [ C ~ ( A U P P ~ ~ ) ( C O ) ~ ( ~ ~ - C ~ H ~ C H O ) 1 two carbonyl groups may be described as semi-bridgir~g~~~ and in [(HB(pzI3) (OC)W(p-CO) (p-CS)Au(PPh3) I CO and CS 1 igands form asymmetric bridges from W to Asymmetrically bridging CO groups to Cu are also found In [ ( M ~ C ~ ( ~ Z ) ~ ) M O ( ~ - C O ) ~ C U ( P P ~ ~ ) ] . ~ ~ ~ In complexes [Os(p-(Ctol)) (MCl )Cl(CO)- (PPh3l21 (M - Cu, Ag, Au) a dimetallacyclopropene unit, Os-C-M, involves a coinage meta 1 .361

Formally there is a M X o triple bond in complexes [CpM(p-C0)3Co(n4-C4Me4) I (M = Mo, U)345 but these species may be considered as analogues of sandwich complex [CpCo(o4-C4Me4)1, with [COM(CO)~I- being isolobal with CpT Other characterised complexes containing related group VI metal entities and formal double metal-metal bonds are [Cp(C2H4 )W (@-C0I2Pt (PR312 1: prepared by protonation with HBF4.Et20 of precursor complex with (p-CMe) 1 igand, 348 [ (MeGa(p~)~)MoRh (fi-CO), (CO) (PPh3 )2 1334 and [CpURh(p-C0)2L(PPh3 12 I . 342 Reaction of [Fe(tl6-C6Mg)2] with [CpM(C0)2] (M - CO, Rh, Ir) affords unsaturated complexes [06-CgH6)Fe(p-Co)2MCp] with formal Fe-M double bonds.447

[CpM(a-HI2h-n5:n1-C5H4)IrH(PMePh2 l2 1' (M I Mo, U) are formed by elimination of H2 from [Cp2MHZl and [IrH2(~0lvent)~- L,]? 335 Hydride bridges are also present in structurally characterised [MnPt(p-H)(p-CO)(CO)4(PEt3)2 1338 and [RuRh(p-H)(p-Cl )(dppm)2(cod) I? 359 Photo- induced insertion of alkene and CO into the hydrogen bridge of [MoMn (p-H) (p-PPh2 ) (CO )6cp ] produces p-n1 : (C,O )-acyl species [MoMn (p-OCR 1- (j~-PPh~l(C0)~Cp] which adds CO with cleavage of Mo-Mn bond and flipping of p-OCR co-ord i na t ion mode.

The $,n2-bound acyl complex [MoFeIp-OC(tol)) (p-CO)(CO)(NO)Cp21 is formed from anionic acyl monomer [Cp(OC)(NO)Mo-C(OLi 1 (to1 11- and [Cp(OC)2Fe(THF) It with migration of acyl from Mo to Fe.332 The organic bridge in [ZrRu(p-OCCH2- CH2C5H4 ) ( p-CO ) (CO )Cp2 ] may be cons i dered to be a ti rconoxycarbene bound to Ru or a Zr-complexed Ru-acyl moiety.323 The thioacyl ligand in [MoFe(p-SC(to1)) (CO)5Cp] is produced by the action of sulphur on a precursor p-C(to1 I complex.331

Unsaturated complexes [UFe(p-CR)(CO)nLI (L - HB(pz)3, Cp* or Cpt n - 5) reversibly add CO to give 34-electron species (n - 6)3411342#442 and the related saturated MoFe analogue (L = Cp, n - 6) is also i s o l a b i e ~ ~ ~ ~ methylene, from CH2N2, adds to these systems forming p-RC-CH2 ligands331f442 and other transformations of K-CR 1 igands Involving reactions with sulphur, oxygen331 and PPh2H342 are also reported. Other p-alkyl idyne complexes described include derivatives of WRh, 381 WPt348t 381 and UCu. 388 Terminal aikylldyne 1 igands in complexes [RCER~M(CO)~] (M = Cr, Mo, W ) can be converted into p-alkylidene,

- 7

Hydrido-bridged binuclear complexes

180 Organome t a l k Chemistry

pvinyl, palkyl and k-acyl groups339 and also be incorporated as w3-CR bridges in cluster^.^^^^ 377 In [Cp2Ti (p-CH2 (p-Me)Rh(cod) I the Rh-bound methyl groups form an agostic C-H interaction with Ti.322

cores are produced by attack of [Re(C0)5]- on cations [CpMoLL' (RCnCR)]? 330 [Fe2(C0191 reacts with [CpRh(PPrj)- (PhCgH) 1 to form [CpRhFe(N-C-CPHh)(fi-CO) (COl3(PPrl) 1 and [CpRhFe(p-n1,n3- CHCPhCO)(CO)3(PPr~)I.353 Exchange of a CO(CO)~ unit in [CO~(IL-C~(CF~)~) (CO161 by Mo(COI2Cp affords heteronuclear complex [CpMoCoIp-C2 (CF3)2} (COI5

[ (OC 1 3Fe (p-n3 : n4-C7H7 )Rh (cod 1 I promotes carbonyl bridging and a change in C7H7 bonding mode to form [(OCI2Fe(p-n4: n3-C7H7) (p-CO )Rh (PR3 12 1. 354

Binuclear complexes with two bridging dppm ligands are reported for systems with MnPt,445 IrRh,269 PdPt,365 and MoRh440 bonds - the latter complex [M~Rh(fi-CO)(p-SO~)(j~-dpprn)~Cl (C0I2 1 also containing an @-SO2 bridge. Single dppm bridges are present in FeRh,352 FePt352i355 and systems. 2- d i pheny 1 phosph inopyr id i ne bridges connect bonded meta 1 s in [MoPd (~Ph2Ppy 12-

Two phosphide bridges 1 ink Th-Pt in [Cp;Th(1-PPh2l2Pt(PMe3) 1321 and related derivatives of ZrM (M 5 Ni, Pd, Pt)438a and ZrRh324 may possess metal-metal interactions. Several other reports of metal-metal bonded phosphide bridged complexes have appeared. 336 I 346 I 3 5 6 ~ 358 1 438b1 439 443 The 1,3-diphospha-4- metal labutadiene [Cp(OC12W=PRCH-PR I acts as a 1 igand to Fe in [Cp(OC)2WFe-

Tetrahedrane complexes with MoRe (p-02-C2R2

Phosphine substitution of cod in

( p-co 1 (CO 12 1.337

(1-PRCHPR (CO I. 343 [Few (p-n2-Se2) (CO18 12+ has a tetrahedral core structure. 340

3.2 Tri- and Hiaher Nuclearitv ComDlexes. - Clusters structurally characterised by X-ray diffraction are listed in Table 2 . Limitations of space prevent a full discussion of all these heteronuclear systems.

The heteronuclear carbonyl anion [Fe4Ru2(C0)22 12- adopts a structure comprising two vertex connected Fe2Ru triangles393 whereas [Fe3Rh3 (p-CO17- (CO)10]3- consists of an Fe2Rh3 trigonal bipyramid spiked by Fe at the apical Rh atom.403 Capping of reactive carbonyl cluster [RUCO~(CO)~~I by metal and non-metal reagents is a route to new tetra- and tri-nuclear heter~clusters.~~~

Reaction of [Mn(CBr3)(CO)51 with [PPNI[Co(CO141 yields ketenylidene cluster [MnCo2(p3-CCO) (C0lg IT 38g A thiocarbonyl bridge contributes six-electrons to the bonding in [Cp(OC)2FeCo3(~4-CS)(~-CO~2(CO~51 which has an Fe spiked C O ~ triangular core. 398 A reduced C02 bridge is found in complex 1 (PMe2PhI30sRh2- (1r3-CO2 1 (P-H 12 (cod 12 1. 412

Characterised tetrahedral clusters containing cyclopentadienyl ligands include [CPMOI~~(~~-CO)~(COI~ 1374 and phosphine substituted clusters [CpNiOs3- (fi-H)3(CO)9-nL,1 (1 - 1,2).413a414 Hydrogen initiated reactions of [CpMo-

0

4 2

TABLE

2.

X-RA

Y DETERMINED STRUCTURES OF HETEROMETALLIC TRI- A

ND HIGHER NUCLEARITY COMPLEXES.

MANGANESE

AND

RHENIUM

[MnCo,(r,-CCO)

(p-C

O) (CO)81- 389

[Re3

Au (p-H)

(CO) (

PPh3) 1

- 390

[ Re7Au ( p6-C) (CO) 21 (PPh3) ] 2-

391

3 -

9

IRON

[ FeRuZ

( p3

-W

(a

3-CO

) (C

O) (

P (On

e) )

1 392

[Fe4

Ru2 (

CO) 22]2- 393

IFeRuCo, (p4-C

2Ph)

(p-CO) (CO) 9Cp]3

83

[FeR

uCoI

r (p4-

PMe)

(p-H) (C

O) loCp

] 394

' R' IFeRu3(P4-N) (CO)lo(P(O~e)3),]-

392

9 3 8 0

[FeRuCoRh, (p4-P

Me) (

p3-H

) (p-co) (co

) 7cp2]

394 t E

[F

e2Co

(p3-

COMe

) (p

-H) (C

O)7C

p]395

E' %

[ FeCo, (

p3-

BUtP

(C=C

HPh)

) (C

O) 9

] 39

7 7

[FeCoNi(p3-q2-C2Et,) (CO),Cp]

399

P i!- 8'

[FeCo,(r3-s)2

(NO),CPZ~I~~~

4 2 [F

eCo3

(p4-

Cs) (r

-co)

(co

) ,cp

] 398

[FeC

oNi(

fi3-

q2-C

2Ph2

) (p-

co) (CO),CP]~~~ '

[ Fe2

CoAu

( f13

-COMe

) (p

3 -CO)

(CO)

( PPh3

) Cp] 39

5

[ Fe2

Rh (p3

-COM

e) ( p-H)

( CO)

,Cp ] ,0°

[ Fe3Rh

( p4

-PPh

) , (co

) 9cp

*] 401

[Fe,Rh(r,-PPh),(r-CO)

, (CO)

6cp*]401

[Fe3Rh, (p4-r12-MeC=C=CH2) (p-co)

(co)

,02

[Fe3m3 (r-co) , (c

o)

403

[FeZNi

(p3-

COMe

) (p

3-co

) (co)~c~]

395

[Fe3Cu

3 (co

) 12] 3

- 4

04

[Fe4

C~5(

co)1

6]3-

404

IFe4Au2 (p

6-BH

) (CO

) 12 (P

Ph3)

2] 405

TABL

E 2

(continued)

COBA

LT

[co,

~,(~

,-~~

-c,(

c~F~

),) (

~-co),(co)~I~~~

[Co2

Ni (p3-

COOM

e) (CO) 6cp]

301

[CoN

i2 (p,-COOMe) (CO

) 3cp,] 301

IRIDIUM

[ Ir4

Au2 (

p3

- ( PhPPPh) 1r

4 (CO) 11

-

PLATIN

UM

I Pt3

Au (P-

CO) , (r-s

o2

1 (PCY, 1

I+

433

[P~~AU,(PP~~)~(CNC~H~M~,-Z,~)~]~+

434

[ PtAu6 (C,But)

( PPh31

1' 435


(C0),l2 with [OS~H~(CO)~~] yield both tetrahedral [C~MOOS~(~-H)~(CO),~] and tr igonal b ipyramida 1 [Cp2M020s3 (p-H l 2 (CO Il2 I. 373 React ions of carbonylmetalate anions with [Pd2(p-C5H5)(p-X)(PR3)21 (X = halide, carboxylate) afford trinuclear species [LnMPd2 (p-CgH5 1 (K-CO)~ (PR3 12 1 {LnM = V (Cold, CO (CO 12 or CpM' (B~-CO) (M' = Cr, MG, W));375 further displacement of the cyclopentadienyl bridge forms known clusters [Cp,M'2Pd2(p3-C0)2(p-C0)4(PR3)21 (M' = Cr, Mo, W ) I 375 a related Mo2Pd2 species is reported elsewhere.376 Indenyl cluster [Ir2Pt(C0)3(PCy3) (v5-CgH7)21 is

Alkyne bridged clusters [CpNiCoM(p3-rt2-RC2R)(CO)6] (M - Fe, Ru, 0s) are non-rigid and exhibit alkyne rotation on the face of the metal triangle.399 Tetranuclear clusters [Co2Rh2(p4-RC2R) (I-CO)~(CO)~ 1 undergo regiospecif ic fragmentation with CO to give [CoRh(p-v2-RC2R) (CO)61.425 The reversible interconversions of a l k y n e + v i n y l i d e n e * a l k y l i d y n e on a MoRuCo cluster are reported:204b the formation from RCXH of related vinyl idene clusters of the type [C~MCOMI(~~-C-CRH)(CO)~I (M = MO, W $ M I = Fe, R U ~ R = B U ~ ) generates two chiral centres diastereospecifical ly.382 Vinyl idene complexes [Cp(OCI2Mn- (p-C-CPhH)PtL2] act as four-electron ligands to Fe(C0I3 units obtained from reaction with [Fe2(CO)g].449 Coupling of intermediate vinylidene and ethylidyne ligands occurs in formation of 3-methyl-3-allenyl complex [Fe3Rh2- (p4-n3-MeC-C-CH2 1 (cc-CO)~ (COI10 1- 402

Oxidative decarbonation of acetyl ide 1 igand in [ C O ~ { ~ - ~ ~ - P ~ C = C M ( C O ) ~ C ~ I - (COI6l affords [CPMCO~(~~-CP~)(CO)~] (M = Fe, Ru).~~' Addition of Os-CH2 bond from [Os3(p-CHZ) (CO)ll I t o Pt(0) affords spiked triangular cluster [Os3Pt- (p-CH2) (CO)11(PPh3)21.416

Further applications of terminal alkylidyne complexes of the general type [LW(ECR)(CO)~] (L = Cp, Cp* or R'B(pzl3r R = tol, Me or Ph) are reported in the syntheses of the following bridging alkyl idyne clusters: [CpWOs3(p3-C(tol))- (p-H)2(C0)12 I with a triangular Os3 core and pendant CPW(CO)~ tr i nuc 1 ear [Rh2W (r3-CR (K-CO (Co 12-

(?J-C~H~)~(HB(PZ)~} 3 and [FeRhW(p3-CR) (N-CO) (CO)~(~-C~H~){HB(PZ)~} 1: 381 [MU2- (K-CR)~(CO)~L~] (M = Ni, Pt; L - Cp, Cp*).386 Reactions of the latter clusters with [Pt (cod)2 ] afford tetranuclear [MPtWz (p3-CR) (c(-CR) (Cold (cod)L2 1 or pentanuclear (M = Pt) [Pt3W2(p3-CR)2(CO),(cod)2L31386 both of which react with further [LW(ECR)(CO)~] eliminating cod and giving, respectively, [Pt2W3(p3-CR)-

(p-CRI2 (co)~L~ 1386 or seven atom chain species [ P ~ ~ U , ( ~ ~ - C R ) ~ ( ~ - C R I ~ ( C O ) ~ - Similar condensation reactions with [Pt(C2H4)31 or [Ni produce

heteronuclear star-shaped clusters [M2Pt2W4(p3-CR)3 (p-CR) (co)BCp4 1 (M - Pt, 387 Ni385) and [Ni,Pt2U4(p3-CR)4(CO)8Cp41385 containing eight membered metal rings. The binuclear terminal alkylidyne complexes [ReMkCR)(CO)gl (M = Cr, MO or W) are also useful for syntheses of heteroclusters [MReFe(p3-CR)- (p-CO) (cO)ll 1, 369 [ReWPt (p-CR 1 (CO)11-n(PR3 1377 and IN'M2Re2 (P-CR)~ (CO)18 1

c 1 usters [CO~W (p3-CR 1 (CO 18 { R ' B ( pZ 3 1 1,


(M' - Ni, Pt).377 Metal exchange reactions on trinuclear iron395e400 and cobalt301r451

complexes produce various p3-alkylidyne heteroclusters including [CpMFe2- (K~-COM~)(CO)~] (M = Co, Rh, Ni )395t400 and [Cp2MoCoNi ( ~ ~ - C C O ~ P ~ ) ( C O ) ~ I S ~ ~ ~ ~ the separation of pure enantiomersof the latter species has been achieved and the resolution of related chiral clusters with optically active ligands is also discussed.451 Transformations of [Fe2U(p3-CR) (p-CO) (co)8cp] include substitution of CO groups by ~0,379 reactions with [CpW(=CR)(C0)2] giving, inter &a, alkylidyne coupled ligands, 378 and reactions with PHRl from which saturated and unsaturated products [Fe2W (p3-CR 1 (K-H 1 (p-PRi) (C0)nCP I (n - 7 or 6) are obtainable. 380 Phosphido bridged complexes ICo~ll(p3-CR)- (p-H)(p-PRi)(CO)&p] react with PRiH or R'C=CR' mainly by processes involving formation of P-C, C-C and C-H bonds.344

Oxo-capped cluster [Cp;Mo2Fe(p3-O) (CO171 is ~haracterised.~~' Two triply bridging sulphido caps are present in [Cp;Co2Fe(p3-S l2 (NO12 1396 and clusters [CpjV2(MLn)(~3-S)2(r-n2_S2) I {ML, - Fe(C013, Fe(N0I2, CoCp, IrCl (PPh3)) and [Cp4V4Ni (i3-SI4 ( p n 2 - S 2 l2 1 are reported. 367 Framework positional isomers of [CpMoFeCo2(p3-E)(p-AsMe2) (COI8 I (E - S, PMe) are i ~ o l a b l e . ~ ~ ~ Sulphido clusters with PtOs, cores are structurally characterised for !I-= 3, 4 or 5 (see Table 21.4178418 Substitution of four CO ligands on [Cp2M02Fe(p3-Te)2(CO)71 by RCZH converts the Mo2FeTe2 framework from an orachno to closo geometry. 371

A product of protonation of [F~RU~(~,-N)(CO)~~L~I- {L - CO, P(OMe)31 under CO is [FeRu2 (p3-NH) (13-CO) (CO)8Ll, formed via intermediate tetranuclear imido cluster. 392 Preparations of hetero-trinuclear p3-phosphinidene clusters are described147bg451b and additions of RhCp or IrCp fragments to such MM1M2(rr3-PR) clusters afford tetra- and penta-nuclear species such as [CpIrRuCoFe (p4-PR)-

(p-H) (CO)lo 1 and lCp2Rh2FeRuCo (q-PR) (p3-H) (CO 18 1. 394 Unsaturated cluster [C~*R~F~,(K~-PP~)~(CO),,] (5 - 8) reversibly binds CO to form species (fl - 9) with minimal change iz RhFe3P2 framework.401 Pentanuclear [Cp2Ni2Ru3(cc5-PPh)- (CO)g] has an open square-pyramidal metal structure.409 In heterocluster [CrCo,{p3-AsCr(CO)5)2(CO~lo 1 an opened CrCo2 triangle, bridged by two p3-As

atoms, acts as a ligand to two Cr(C015 units.263 A phosphaal lene bridge is present in [FeCoZ(p3-n2-ButPCCHPh) (CO),]397 and a

diphosphane unit 1 inks Ir4Au2 and Ir4 clusters in [Ir4 (CO)llPhPPPhIr4(CO)g- (AuPEt3 l2 I. 431

Several new heteroclusters containing phosphine co-ordinated coinage metal moieties have been reported. In [ C ~ ~ W ~ ( C U P P ~ ~ ) I M ~ - C ( ~ O ~ 1) (C0)41 the CU atom is asymmetrically bridged by alkylidyne ligand.388 Slngle M(PPh3) units (M I Cu, Ag and/or Au) span metal-metal edges in clusters with butterfly cores MFe3410 and MRu32091410 (M = Cu, Ag, Au), AuOs3422e423 and A U C O F ~ ~ , ~ ~ ~ in edge-bridged tetrahedral [Ph3P)AuRu4 (pH13 (C0)12 l4l0 and In edge-bridged

-


trigonal prismatic [ (Ph3P )AUOS~ (jL6-p 1 ( ~ 0 1 ~ 8 1.233 Face capping Au (PR3) units occur in tetrahedral systems [ (Cy3P)AuPt3(g-CO)2(~-L) (PCy3I3 It (L = CO,

and [(Ph3P)AuRe3(~-H)3(CO)nl- (E - 9) formed by CO loss from the thermally unstable butterfly species (21 Face capping by M(PR3) is also observed in trigonal bipyramidal systems MM'Co3 (M - Cu, Au; M' = Fe, 1 2 ~ ) ~ " and C U R U ~ , ~ ~ ' and in capped butterfly AuOs4.420

Clusters [(LmL)M2Ru4H2(C0)121 (M = Cu, Agt L"r = Ph2P(CH2InPPh2 (n = 1-6), Ph2P(CH2)&AsPh2 (n - 1,211 M - Au, r L = dppm) , containing adjacent bridged M2 atoms, have ground state geometries based on capped trigonal bipyramidal or capped square pyramidal cores depending on the nature of the phosphine bridge; these species exhibit fluxional core rearrangements in solution.32*411~452 Triangular cluster [ (Ph3P)2Au2Nb(n5-C5H4SiMe3)2]t is ~haracterised~~~ and in [Pt2Au2(PPh3 l4 (CNC6H3Me2-2, 6 14 12' the metal atoms define a distorted, flattened butterfly with a short Au-Au bond.434

13- have planar metal cores404 and a nearly square planar Ag2Au2 arrangement with Ag-Au interactions is found in [Au2Ag2(~-C2Phl4 (PPh3 l2 A RhAu3 tetrahedron occurs in [ (Ph3PJ3Au3RhH- (PPh3)2(CO)]+ 430 and the Core Of flUXiOnal based on two PtAu4 square pyramids fused at a common PtAu2 face.435

Reported higher nuclearity clusters include [R~,AUC(CO)~~(PP~~ 113- with trans-bicapped octahedral core, 391 [OsgPtZ (CO)16(c~d)2 1, with skeleton of two edge-fused Os4 tetrahedra one of which is Pt-bfcapped, and [OS6Pt2 (C0)16(cOd)- {P(OMe)3)2 I , with bicapped tetrahedron of Os6 having two Pt-capped faces.419 Other skeletal arrangements are the two face condensed octahedra of [PtRh8(CO)19]?- 427 the 3:6:3 triangulated stack of [Ni9Pt3H(C0)21 I?- 432 and Ni-hexacapped Rh5-trigonal blpyramid of [Rh5Ni6Hx(CO)21 13- 426 In clusters [Oslo (ML )C (CO Iz4 I- the Oslo tetracapped-octahedron is edge-br idged (ML - AuPPh3) or face-capped (ML = CuNCMe, AuBr) by the ML moiety:421r424 coupling of cluster with ML = AuBr forms [OS~~AU(C)~(CO)~~]~- with 6:3:3:3:6 stacked metal array.424

185

-

Anions [Cu3Fe3 (COll2 13- and

[(Ph3P)6AU6pt(PPh3)(C2BUt)]' is

4 Comoounds with Bonds between Transition and Main GrOUD Metals

4.1 Lithium. - In solid [{MeN(CH2CH2NMe2)2}Lil[Ni2(pH)(n-C2H4)4] there is an ion-pair contact between Li and one Ni atom of 2.838(3)

4.2 Maanesium. - There are Co-Mg bonds in [COIM~B~ITHF)~) (n3-C3H5)Cpl and in [Co{MgBr(TMED)l (fi-Ph)(n-C2H4)Cpl which also contains a phenyl bridge between the two metals.453

4.3 Mercury. - Complexes with M-Hg-Pt chains are prepared by Pt(0) insertion


into Ar-HgML, bonds (H = Mo, U, Pt) and by exchange between [ H ~ ( P ~ ( c ~ c ~ ~ ) ( P P ~ ~ I ~ ) ~ I and [HgFp21 or [Hg(Mn(CO)5)21.454 A donor-acceptor Fe(0)-Hg(I1) bond is present in [Fe(HgC12)(CS2C2(COOMe)2} (C0)2(PMe2Ph)21455 and HgBr bridges an Os-0s bond in [ C ~ N ~ O S ~ ( ~ - H ~ B ~ ) ( ~ - H ) ~ ( C O ) ~ ( P P ~ ~ H ) I . ~ ~ ~ The two mercury atoms in ~ ~ ~ - [ R U ( C O ) , ( H ~ R U ~ ( ~ ~ - C ~ B U ~ ) ( C O ) ~ ) ~ ] each connect Ru3 triangular clusters to an octahedral Ru atom by bonding to three Ru atoms.456 In [OS~,H~(C)~(CO),~]~- the Hg atom occupies a position in the central layer of the 6:3:3:3:6 stacked array of metal atoms.424 Cluster [ H ~ ~ C O ~ ( C O I ~ ~ I is cleaved to species [CO(H~X)~(CO)~] by compounds HgX2 but is reassembled on addition of PPh3 (when X = ~ 1 1 . ~ ~ ~

4 . 4 Gal 1 ium and Thall ium. - Crystal structures are reported for [Re2(w-GaRe- (C0)5)2(C0)8]458a and [Re2(p-GaRe(C0),(PPh3)) (p-I)2(CO)4(PPh3)21.458b [T16Fel0- (cO)36l6- comprises two coplanar ~1~ triangles each bicapped by two r3-Fe(C0I3 moieties and connected by two r-Fe(C0I4 bridges.459

4 . 5 Grour, IV. - Crystal structures are reported for [Cp*Ta(SiMe3)Cl2LI (L = C1, PMe3), 460 [Cp*IrHZ(SiEt3I2 I , 461 [Os3(p-HI2H(SiHPh2 1 (CO)lo [FpSiMe2- GePh3]463 and [l!(SiF2CBut=CHSiF2)(CO)n(n4-chd)l - (M - U, 1 - 3 ; M = Fe, - n = 2).464 Mechanistic studies of photochemical depolymerisations of [FpSiR2SiR3] to [FpSiR31 and of base induced migrations of polysilyl groups from Fe atom to Cp ring are reported.465

Germylene complexes [Cp*(X)GeW(CO),] (X = C1, alkyl) are described with a crystal structure determination for X - CH(SiMe3)2.466 Compounds M(OArI2 (M = Ge, Sn) form equatorially substituted trigonal bipyramidal complexes [Fe(M (OAr 12) (COI4 I . 467

Linked GeM2 triangles (M - Co, Fe) are present in cluster chain compounds Crystal structure reports of M-Sn bonded complexes include [Cp2TaH2-

(SnMeC12) 1469a and [Cp2MoH(SnMenC13-n) I ( r ~ = 2, 3),469b [ O S ~ ( ~ ~ - H ) ~ ( S ~ M ~ ~ ) ~ - (CO)lo 1462 and [Cp3USnPh3 I .470 Metal loporphyrin systems [ (P)MFe(COI4 1 (M = Ge, Sn; ( P I = OEP, tetraarylporphyrin) exhibit two reversible one-electron reductions without Fe-M bond cleavage.471

A range of trimetallic species [LnM(p-EX2)M’Ln1 (E = Ge, Sn, Pb) are reported for various combinations of carbonyl species MLn/M’Ln (M/M’ = Mn, Fe or R u ) . ~ ~ ~ Two SnCp; molecules act as bridges in [Fe2(p-SnCp;)2(CO)81.473

The cluster [ O S ~ ( S ~ C ~ ~ ) ( ~ - C H ~ ) ( C O ) ~ ~ I has a planar butterfly arrangement for Os3Sn with Sn connected to the three 0s atoms.474 In [Fe21r-Pb(Fe(CO)4 12) (p-CO12 (COI6 12- there is distorted tetrahedral co-ordination to Pb by four Fe atoms.475

[Ge2C04Fe2 (CO 121 I and [Ge3COg (co 126 1. 468

-

- - - -


4.6 Bismuth. - [Bi(Fe(CO),}413- contains a tetrahedrally co-ordinated Bi atom.476 Methylation of [Fe3Bi (CO)lol- by CF3S03Me affords [Fe3(~3-Bi 1- (w3-COMe) (C0lg I ;477 other structurally characterised clusters are [Fej h3-Bi 1- (B-H l 3 (CO l9 I , 477 [Fe3 (19-Bl Iijq-BiFe (C0)4} (CO 19 ]?- 478 [FeZCo (fi3-Bi 2 1 (CO 110 I- 478 and also [Bi4Fe4(C0113]?- now described in a full paper with molecular orb i ta 1 calculations. 479

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191 192 193 194

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240 24 1 242 243 244

245

246 247

248 249

250 25 1 252 253

254

255

256

257 258

259 260 26 1 262

263

264 265 266

261 268 269 270 27 1 272

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Organometallic Compoundr containing Metal-Metal Bona3 195

273

274 275

276

277

278

279

280 28 1

282 283

284 285

286

287

288 289

290 29 1

292 293

294

295 296

297 298

299

300 30 1 302

303

(a) R.A.Jones, T.C.Wright, J.L.Atwood and W.E.Hunter, Acta Crvstalloar, Sect. 6 1986, 294; (b) A.M.Arif, R.A.Jones, M.H.Seeberger, B.R.Whittlesey and T.C.Wright. Inore. Chem., 1986, 25, 3943. T.S.Targos, G.L.Geoff roy and A.L.Rheingold, Qraanometallica, 1986, 5, 12. F.Barcelo, F.A.Cotton, P.Lahuerta. R.Llusar, MSanau, W.Schwotzer and M.A.Ubeda, Oraanometallics, 1986, 5, 808. P.T.Bishop, J.R.Dilworth, T.Nicholson and J.A.Zubieta, J. Chem. SOC,, Chem. Commun, 1986, 1123. A.J.Deeming, MN.N.Meah, HMDawes and MB.Hursthouse, J. Oraanomet. Chem., 1986, a C25. J.H.Bieri, T.Egolf, W.von Philipsborn, U.Piantini, R.Prewo, U.Ruppli and A.Salzer, Oraanometallics, 1986, & 2413. (a) J.A.Abad, Inora. Chim. Act% 1986, 121. 213; (b) W.C.Spink and M.D.Rausch, L Oraanomct, Chem,, 1986, C1; (c) H.J.Scholz and H.Werner, 1986, m, C8. M.J.Krause and R.G.Bergman, Qraqnometallics, 1986, 5, 2097. W.A.Herrmann, E.Herdtweck and C.Weber, Annew. Chem., Int. Ed. E n d , 1986, 2, 563. J.W.Bixler, A.MBond and R.S.Dickson, Qranaometa l l i~ , 1986, z., 1435. (a) R.S.Dickson, G.D.Fallon, S.M.Jenkins, B.W.Skelton and A.H.White, J. Oraanomet, Chem, 1986, 314, 333; (b) C.W.Baimbridge, R.S.Dickson, G.D.Fallon, IGrayson, R.J.Nesbit and J.Weigold, Aust. J . Chem, 1986, E, 1187. W.D.McGhee and R.G.Bergman, J. Am. Chem. SOC., 1986, J.Q&, 5621. H.Brunner, W.Meier, B.Nuber, J.Wachter and M.L.Ziegler, Anaew. Chem, Int. Ed, Enal., 1986, z, 907. L.A.Oro, D.Carmona, MP.Puebla, M.P.Lamata, C.Foces-Foces and F.H.Cano, Inorn. Chim. Act&, 1986, 112. L11. I.M.Saez, N.J.Meanwel1, A.Nutton, K.Isobe, A.V.de Miguel, D.W.Bruce, S.Okeya, D.G.Andrews, P.R.Ashton, 1.R.Johnstone and P.M.Maitlis, J. Chem. SOC., Dalton Trans., 1986, 1565. N.J.Meanwel1, A.J.Smith and P.M.Maitlis, J. Chem. SOC., Dalton Trans., 1986, 1419. (a) A.L.Balch, L.A.Fossett, M.M.Olmstead and P.E.Reedy, Qraanometallics, 1986, I, 1929; A.L.Balch, L.A.Fosset, J.Linehan and M.M.Olmstead, m, p.691; A.L.Balch, L.A.Fosset, R.R.Guimerans, M.M.Olmstcad, P.E.Reedy and F.E.Wood, Inora. Chem., 1986, & 1248; (b) A.L.Balch, L.A.Fossett, R.R.Guimerans, M.M.Olmstead and P.E.Reedy, u, p.1397. R.A.Jones and T.C.Wright, Inora. Chem, 1986, a, 4058. A.M.Arif, R.A.Jones, S.T.Schwab and B.R.Whittlesey J. Am. Chem. SOC, 1986, J.Q&, 1703. A.M.Arif, D.E.Heaton and R.A.Jones, J. Chem. SOC., Chem. Commun., 1986, 1506. R.Ros, A.Scrivanti, V.G.Albano, D.Braga and LGarlaschelli, J. Chem. SOL, Dalton Trans., 1986, 241 1; R.Ros, A.Scrivanti and R.Roulet, J, Oreanomet. Chem,, 1986, m, 273. L.Garlaschelli, M.C.Malatesta, S.Martinengo, F.Demartin, M.Manassero and M.Sansoni, J. Chem. SOL, Dalton Trans, 1986, 777. S.Martinengo, G.Ciani and A.Sironi, L Chem. SOC , Chem. Commun, 1986, 1742. C.Allevi, B.T.Heaton, C.Seregni, LStrona, R.J.Goodfellow, P.Chini and S.Martinengo, J. Chem. SOC., Dalton TranL 1986, 1375. D.L.DeLaet, P.E.Fanwick and C.P.Kubiak, Qrnanometallics, 1986, 5, 1807. RGoddard, C.Kruger, K.R.Porschke and G.Wilke, J. Oraanomet. Chem., 1986, 308, 85. H.Lehmkuh1, F.Danowski, R.Benn, R.Mynott and G.Schroth, Chem. Ber., 1986, 119, 2542. R.A.Jones and B.R.Whittlesey, Inorg. Chem, 1986, a, 852. R.Blumhofer, K.Fischer and H.Vahrenkamp, Chem. Ber., 1986, m, 194. D.F.Rieck, R.A.Montag, T.S.McKechnie and L.F.Dah1, Am. Chem. SOC., 1986, 108. 1330. (a) A.Ceriotti, A.Fait, G.Longoni, G.Piro, L.Resconi, F.Demartin, M.Manassero, N.Masciocchi and MSansoni, L Am. Chem. SOC., 1986, 198, 5370; (b) A.Ceriotti, A.Fait, G.Longoni and G.Piro, F.Demartin, M.Manassero, N.Masciocchi and M.Sansoni, U, p.8091.


304 (a) P.Espinet, J.Fornies, C.Fortuno, G.Hidalgo, F.Martinez, M.Tomas and A.J.Welch, J, OrgpILgmet. Chem .~ 1986, 317. 105; (b) R.Uson, J.Fornies, R.Navarro and J.I.Cebollada, a, 1986, D, 381.

305 A.J.McLennan and R.J.Puddephatt, Orarrno metallic& 1986, & 811. 306 (a) T.Yamamoto, MAkimoto, 0.Saito and A.Yamamoto, Oraanometallics, 1986, 5,

1559; 307 D.P.Bancroft, F.A.Cotton, L.R.Falvello and W.Schwotzer, Inorn. Chem., 1986, a,

763. 308 H.Schollhorn, U.Thewalt and B.Lippert, J. Chem. SOC., Chem. Commun., 1986, 258. 309 (a) Y.Yamamoto, K.Takahashi and H.Yamazaki, J. Am. Chem. Soc,, 1986, 198,

2458; (b) C.E.Briant, D.I.Gi1mour and D.M.P.Mingos, J, Oraanomet. Chem, 1986, 308, 381.

(b) A.Behr, G.V.Ilsemann, W.Keim, C.Kruger and Y.H.Tsay, ibid, p.514.

310 M.F.Hallam and D.M.P.Mingos, J. Oraanomet. Chem,, 1986, U, C35. 31 1 (a) G.Ferguson, B.R.Lloyd and R.J.Puddephatt, m n o m e t a l l i c s , 1986, Z 344; (b)

312 313 314

315 316 317

318

319

320

321

322

323 324 325

326 327

328 329

330 33 1

332 333 334

335 336 337

338 3 39

G.Ferguson, B.R.Lloyd, L.Manojlovic-Muir, K.W.Muir and R.J.Puddephatt, Inora, Chem., 1986, 4190; (c) M.C.Jennings, N.C.Payne and R.J.Puddephatt, J. Chem. Soc., Chem. Commun, 1986, 1809. M.Rashidi and R.J.Puddephatt, J. Am. Chem. SOC., 1986, J.Q&, 7111. C.E.Briant, D.G.Evans and D.MP.Mingos, J. Chem. SOC, Dalton Trans., 1986, 1535. E.G.Mednikov, N.K.Eremenko, Yu.L.Slovokhotov and Yu.T.Struchkov, 1. Oraanomet, Chem., 1986, 2pL, C35. L.C.Porter and J.P.Fackler, Acta Crvstallonr, Sect. C, 1986, a, 1128 and 1646. J.P.Fackler and L.C.Porter, J. Am. Chem. SOC., 1986, 108, 2750. (a) H.H.Murray, J.P.Fackler, L.C.Porter and A.M.Mazany, J. Chem. Soc,, Chem. Commun, 1986, 321; (b) H.H.Murray and J.P.Fackler, Inorn. Chim. Acta, 1986, 115, 207; H.H.Murray, J.P.Fackler, A.M.Mazany, L.C.Porter, JShain and L.R.Falvello, m, 1986, 114, 171. R.Uson, A.Laguna, M.Laguna, M.N.Fraile, P.G.Jones and GMSheldrick, L Chem. Sot., Dalton TranL, 1986, 291. E.Wehman, G.van Koten and J.T.B.H.Jastrzebski, J. Organornet. Chem,, 1986, 302. c35. W.Bos, R.P.F.Kanters, C.J.van Halen, W.P.Bosman, H.Behm, J.MM.Smits, P.T.Beurskens, J.J.Bour and L.H.Pignolet, J. Oraanomet. Chem., 1986, 307 385. P.J.Hay, R.R.Ryan, K.V.Salazar. D.A.Wrobleski and A.P.Sattelberger, J. Am. Chem. & 1986, 108, 313. J.W.Park, P.B.Mackenzie, W.P.Schaefer and R.H.Grubbs, J. Am. Chem. SOC., 1986, 108, 6402. C.P.Casey, R.E.Palermo and A.L.Rheingold, J. Am. Chem. SOC, 1986, 108, 549. R.T.Baker and T.H.Tulip, Oraanometallics, 1986, 2, 839. L.W.Arndt, MY.Darensbourg, T.Delord and B.T.Bancroft, J. Am. Chem. SOC., 1986, 108, 2617. R.B.King, W.K.Fu and E.M.Holt, Inora. Chem, 1986, a, 2394. W.A.Herrmann, J.Rohrmann, E.Herdtweck, C.Hecht, M.L.Ziegler and O.Serhadli, L Oraanomet. Chem., 1986, 314, 295. F.Edelmann, S.Tofke and U.Behrens, J. Oraanomet. Chem, 1986, 309, 87. T.Adatia, K.Henrick, A.D.Horton, M.J.Mays and MMcPartlin, ,L Chem. SOC,, Chem. Commun., 1986, 1206. W.Beck, H.J.Muller and U.Nage1, Anaew. Chem., Int, Ed. E n d , 1986, a, 734. M.E.Garcia, J.C.Jeffery, P.Sherwood and F.G.A.Stone, J . Chem. SOC.. Chem, Commun, 1986, 802. P.V.Bonnesen, A.T.Baker and W.H.Hersch, J. Am. Chem. SOC., 1986, 108, 8304. S.D.Jensen, B.H.Robinson and J.Simpson, Oraanometallics, 1986, 5, 1690. G.A.Banta, B.M.Louie, E.Onyiriuka, S.J.Rettig and AStorr, Can. J. Chem., 1986, 64, 373. A.Albinati, A.Togni and L.M.Venanzi, OraanometallicS, 1986, Z 1785. S.J.Loeb, H.A.Taylor, L.Gelmini and D.W.Stephan, &.QQZ. Chem., 1986, a, 1977. Z.Z.Zhang, H.K.Wang, H.G.Wang and R.J.Wang, J. Oraanomet. Chem., 1986, 314, 357. O.Bars, P.Braunstein, G.L.Geoffroy and B.Metz, Oraanometallics, 1986, 5, 2021. J.C.Jeffery, A.G.Orpen, F.G.A.Stone and M.J.Went, J. Chem. SOC,, Dalton TranL, 1986, 173.

Organometallic Compounch containing Metal-Metal Bonds 197

340 34 1

342

343

344 345

346

347

348 349

350 351

352

353 354

355 356 357

358 359

360

36 1

362

363

364

365

366

367

368

369

370 37 1 372

373 374

315 316

D.J.Jones, T.Makani and J.Roziere, J. Chem, SOC., Chem. Commun., 1986, 1275. MGreen, J.A.K.Howard, A.P.James, A.N.de UJelfs , C.M.Nunn and F.G.A.Stone, L Chem. So&, pal ton TranL, 1986, 1697. S.V.Hoskins, A.P.James, J.C.Jeffery and F.G.A.Stone, J. Chem. SOC., Dalton Trans,, 1986, 1709. H.H.Karsch, H.U.Reisacher, B.Huber, G.Muller, W.Malisch and K.Jorg, Annew. Chem.. Int. Ed. En&, 1986, 25, 455. P.Dunn, J.C.Jeffery and P.Sherwood, L, Oraanomet. Chem., 1986, 311. C55. P.Hartner, H.Pfisterer and M.L.Ziegler, AnQeW. Chem., Int. Ed, Ennl,, 1986, 2, 839. S.Rosenberg, W.S.Mahoney, J.M.Hayes, G.L.Geof f roy and A.L.Rheingold, Oraanometallicg, 1986, z 1065. J.H.Davis, P.G.Lenhert, C.M.Lukehart and L.A.Sacksteder, Acta Crvstallogr, Sect. C, 1986, a, 1133. M.R.Awang, J.C.Jeffery and F.G.A.Stone, J. Chem. SOC., Dalton Trans., 1986, 165. H.P.Kim, S.Kim, R.A.Jacobson and R.J.Angelici, J. Am. Chem. So c , 1986, 108, 5 154. A.L.Rheingold, W.K.Meckstroth and D.P.Ridge, InorP Chem, 1986, 25, 3706. F.W.B.Einstein, P.Manning, L.K.Petersen and K.G.Tyers, ho rn . Chim. Acta, 1986, 111, L49. G.B.Jacobsen, B.L.Shaw and M.Thornton-Pett, J. Chem. SOC, Chem. Commun, 1986, 13. H.Otto, F.J.G.Alonso and H.Werner, J. Oraanomet. Chem., 1986, m, C13. R.G.Bal1, F.Edelmann, G.Y.Kie1, J.Takats and R.Drews, Oraanometallicg, 1986, 5, 829. G.B.Jacobsen, B.L.Shaw and M.Thornton-Pett, Inore. Chim. Acta, 1986, JJJ, L1. R.Regragui, P.H.Dixneuf, N.J.Taylor and A.J.Carty, Qraanometallics, 1986, 5, 1. S.Guesmi, P.H.Dixneuf, N.J.Taylor and A.J.Carty, J. Oraanomet. Chem,, 1986, 303. c47. S.Guesmi, N.J.Taylor, P.H.Dixneuf and A.J.Carty, Oraanometallics, 1986, 2, 1964. B.Delavaux, B.Chaudret, F.Dahan and R.Poilblanc, J. Oraanomet. Chem., 1986, 317, 69. B.Delavaux, BChaudret, J.Devillers, F.Dahan, G.Commenges and R.Poilblanc, L Am. Chem. SOC,, 1986, 198, 3703. G.R.Clark, C.M.Cochrane, K.Marsden. W.R.Roper and L.J.Wright, J. 0 rnanomet Chem, 1986. U, 211. D.A.Roberts, W.C.Mercer, G.L.Geoffroy and C.G.Pierpont, Inore. Chem, 1986, z, 1439. A.A.Del Paggio, E.L.Muetterties, D.M.Heinekey, V.W.Day and C.S.Day, OrnanometallicS, 1986, 2, 575. B.D.Alexander, B.J.Johnson, S.M.Johnson, A.L.Casalnuovo and L.H.Pignolet, J; Am, Chem. SOC, 1986, 1ps, 4409. J.Fornies, F.Martinez, R.Navarro, A.Redondo, M.Tomas and A.J.Welch, L Oraanomet. Chem, 1986, 316. 351. R.Uson, J.Fornies, M.Tomas, J.MCasas, F.A.Cotton and L.R.Falvello, Inorn. Chem,, 1986, a, 4519. C.M.Bollinger, T.D.Weatheril1, T.B.Rauchfuss, A.L.Rheingold, C.S.Day and S.R.Wilson, Inora. Chem,, 1986, 25, 634. M.Fajardo, M.P.Gomez-Sal, P.Royo, S.M.Carrera and S.G.Blanco, I. Oraanomet Chem, 1986, 312. C44. D.G.Evans, J.A.K.Howard, J.C.Jeffery, D.B.Lewis, G.E.Lewis, M.J.Gosse-Ophoff, M.J.Parrott and F.G.A.Stone, J. Chem. SOC., Dalton Trans., 1986, 1723. C.P.Gibson, J.S.Huang and L.F.Dah1, Qraanometallics, 1986, 2, 1676. L.E.Bogan, G.R.Clark and T.B.Rauchfuss, ho rn . Chem,, 1986, a, 4050. M.Muller, H.T.Schacht, K.Fischer, J.Ensling, P.Gutlich and H.Vahrenkamp, Znorq. Chem, 1986, 2, 4032. L.Y.Hsu, W.L.Hsu, D.Y.Jan and S.G.Shore, Draanometallics, 1986, 2, 1041. M.R.Churchil1, Y.J.Li, J.R.Shapley, D.S.Foose and W.S.Uchiyama. J, 0 rnanomet Chem, 1986, U, 121. H.Werner, P.Thometzek, C.Kruger and H.J.Kraus, Chem. Ber, 1986, 2777. H.P.Abicht, R.Barth, K.Peters, E.M.Peters and H.G.von Schnering, 2. C hem,.


1986, 2, 409. J.C.Jeffery, D.B.Lewis, G.E.Lewis, M.J.Parrott and F.G.A.Stone, J. Chem. SOC., Dalton TranL, 1986, 1717. E.Delgardo, J.C.Jeffery and F.G.A.Stone, J. Chem. SOC., Dalton Trans., 1986, 2105.

Trans., 1986, 869.

377

378 379 E.Delgardo, J.C.Jeffery, N.D.Simmons and F.G.A.Stone, J. Chem. SOC., Dalton

380 J.C.Jeffery and J.G.Lawrence-Smith, J. Chem. SOC., Chem. Commun., 1986, 17. 381 M.Green, J.A.K.Howard, A.P.James, C.M.Nunn and F.G.A.Stone, J. Chem. SOC.,

Dalton Trans., 1986, 187. 382 C.von Schnering, T.Albiez, W.Bernhardt and H.Vahrenkamp, Anpew. Chem., Int.

Ed. Enal,, 1986, E, 479. TRoland , W.Bernhardt and H.Vahrenkamp, Chem, Ber,, 1986, 119, 2566. Y.Chi, J.R.Shapley, M.R.Churchil1 and Y.Li, Inora. Chem., 1986, 2, 4165.

Ed. E n d , 1986, 25, 190.

&&, Dalton Trans,, 1986, 2091.

383 384 385 G.P.Elliott, J.A.K.Howard, T.Mise, C.M.Nunn and F.G.A.Stone, Annew. Chem., Int. 386 G.P.Elliott, J.A.K.Howard, T.Mise, I.Moore, C.M.Nunn and F.G.A.Stone, J. Chem.

387 G.P.Elliott. J.A.K.Howard, C.M.Nunn and F.G.A.Stone, J. Chem. SOC., Chem. Commun., 1986, 431.

388 M.Muller-Gliemann, S.V.Hoskins, A.G.Orpen, A.L.Ratermann and F.G.A.Stone,

389 3 90

39 1 392 393 394 395 396 397

398

399 400 40 1 402 403

404 405 406 407

408

409

410

41 1

412 413

414

415 416

Polyhedron, 1986, 5, 791. A.M.Crespi and D.F.Shriver, Oraanometallics, 1986, 2, 1750. T.Beringhelli, G.Ciani, G.D'Alfonso, V.D.Malde and M.Freni, J. Chem. Soc., Chem. Commun, 1986, 735. T.J.Henly, J.R.Shapley and A.L.Rheingold, 1. Ornanomet. Che mr, 1986, 310, 55. M.L.Blohm, D.E.Fjare and W.L.Gladfelter, J. Am. Chem. SOC, 1986, 10$, 2301. F.R.Furuya and W.L.Gladfelter, J. Chem. SOC., Chem. Commun., 1986, 129. D.Mani and H.Vahrenkamp, Chem. Ber., 1986, 119, 3649. A.A.Aitchison and L.J.Farrugia, OraanometallicS, 1986, 5, 1103. D.Seyferth, MK.Gallagher and M.Cowie, Oraanometallics, 1986, 539. R.Mathieu, A.M.Caminade, J.P.Majora1 and J.C.Daran, L Am. Chem. SOC., 1986, 108, 8007. L.Busetto, V.Zanotti, V.G.Albano, D.Braga and M.Monari, J. Chem. Soc,, Dalton Trans,, 1986, 1791. F.W.B.Einstein, K.G.Tyers, A.S.Tracey and DSutton, Inora. Chem,, 1986, 2, 1631. L.J.Farrugia, J. Oraanomet. Chem., 1986, 310, 67. H.H.Ohst and J.K.Kochi, OraanometallicS, 1986, 3, 1359. S.Attali, F.Dahan and R.Mathieu, Ornanometallics, 1986, 5, 1376. A.Ceriotti, R.D.Pergola, G.Longoni, B.T.Heaton, F.Demartin and M.Manassero, L Qrganomet. Chem,, 1986, 311, C31. G.Doyle, K.A.Eriksen and D.Van Engen, J. Am. Chem. SOC, 1986, 108, 445. C.E.Housecroft and A.L.Rheingold, J. Am, Chem. SOC., 1986, 108, 6420. J.Pursiainen and T.A.Pakkanen, J. Ornanomet. Chem,, 1986, 309. 187. P.Braunstein, J.Rose, A.Dedieu, Y.Dusausoy, J.P.Mangeot, A.Tiripicchio and M.Tiripicchio-Camellini, J. Chem. SOC., Dalton T r a m , 1986, 225. J.Pursiainen, T.A.Pakkanen, B.T.Heaton, C.Seregni and R.G.Goodfellow, J. Chem. u, Dalton Trans., 1986, 68 1; J.Pursiainen and T.A.Pakkanen, J. Oraanomet. Chem, 1986, U, 353. M.Lanfranchi, A.Tiripicchio, E.Sappa and A.J.Carty, J. Chem. SOC., Dalton Trans., 1986, 2737. R.A.Brice, S.C.Pearse, 1.D.Salter and K.Henrick, J. Chem. SOC., Dalton Trans,, 1986, 2181. P.A.Bates, S.S.D.Brown, A.J.Dent, M.B.Hursthouse, G.F.M.Kitchen, A.G.Orpen, 1.D.Salter and V.Sik, J. Chem. S&, Chem. Commun,, 1986, 600. E.G.Lundquist, J.C.Huffman and K.G.Caulton, J.m. Chem. SOC, 1986, 108, 8309. G.Predieri, A.Tiripicchio, C.Vignali, ESappa and P.Braunstein, J. C hem. SOC., Dalton Trans,, 1986, 1135. E.Sappa, M.L.N.Marchino, G.Predieri, A.Tiripicchio and M.T.Camellini, L Ornanomet. Chem, 1986, 307, 97. M.I.Bruce, M.R.Snow and E.R.T.Tiekink, Aust. J. Che m,, 1986, 2145. G.D.Williams, MC.Lieszkovszky, C.A.Mirkin, G.L.Geoffroy and A.L.Rheingold,

Organometallic Compounh containing MetaCMetal Bonds 199

417 418 419 420

42 1

422

423 424

425 426

421 428 429

430 43 1

432

433 434 435

436 437 438

439 440 44 1 442

443 444 445 446 447 448 449

450 45 1

452 453 454

455

456 457 458

OrnanometallicL 1986, 2, 2228. R.D.Adams, 1.T.Horvath and S.Wang, Inora. Chem, 1986, z, 1617. R.D.Adams, J.E.Babin, R.Mathab and S.Wang, Inora. Chem., 1986, a, 1623. C.Couture and D.H.Farrar, J, Chem. SOC., Dalton Trans , 1986, 1395. J.Puga, R.A.Sanchez-Delgardo, J.Ascanio and D.Braga, J. C hem. SOC,, Chem, Commun,, 1986, 1631. B.F.G.Johnson, J.Lewis, W.J.H.Nelson, M.D.Vargas, D.Braga, K.Henrick and M.McPartlin, J. Chem. SOC, P a lton Trans , 1986, 975. A.J.Deeming, S.Donovan-Mtunzi and K.Hardcastle, J. Chem. SOC., Dalton TranL, 1986, 543. L.J.Farrugia, Acta Crvstalloer, Sect. C, 1986, 680. S.R.Drake, K.Henrick, B.F.G.Johnson, J.Lewis, M.McPartlin and J.Morris, J, Chem. Soc., Chem. Commun., 1986, 928. I.T.Horvath, L.Zsolnai and G.Huttner, Oraanometallics. 1986, 5, 180. D.A.Nagaki, J.V.Badding, A.M.Stacy and L.F.Dah1, J. Am. Chem. SOC,, 1986, 148, 3825. A.Fumagalli, S.Martinengo, G.Ciani and G.Marturano, Inora. Chem., 1986, a, 592. S.L.Schiavo, G.Bruno, P.Piraino and F.Faraone, Oraanometallics, 1986, 2, 1400. M.A.Ciriano, L.A.Oro, J.J.Perez-Torrente, A.Tiripicchio and M.Tiripicchio-Camellini, J. Chem. SOC., Chem, Commun, 1986, 1737. P.D.Boyle, B.J.Johnson, A.Buehler and L.H.Pignolet, Inora. Chem,, 1986, 5. J.N.Nicholls, P.R.Raithby and UD.Vargas, J. Chem. SOC., Chem. Commun., 1986, 1617. A.Ceriotti, F.Demartin, G.Longoni, M.Manassero, G.Piva, G.Piro, MSansoni and B.T.Heaton, J. Oraanomet. Chem., 1986, 301. C5. D.M.P.Mingos and R.W.M.Wardle, J. Chem. SOC., Dalton Trans., 1986, 73. C.E.Briant, D.I.Gilmour and D.M.P.Mingos. J. Chem. SOC., Dalton Trans., 1986, 835. D.E.Smith, A.J.Welch, LTreurnicht and R.J.Puddephatt, Inora. Chem,, 1986, E, 4616. 0.M.Abu-Salah and C.B.Knobler, J. Oraanomet. Chem., 1986, 302. C10. B.A.Kelsey and J.E.Ellis, J. Am. Chem. SOC., 1986, m, 1344. (a) L.Gelmini and D.W.Stephan, Inora. Chem,, 1986, 22 1222; (b) S.Rosenberg, S.P.Lockledge and G.L.Geoffroy, Oraanometallics, 1986, 5, 25 17. T.S.Targos, G.L.Geoff roy and A.L.Rheingold, Oraanomet. Chem, 1986, m, 223. W.A.Schenk, 7. Natu rf o r sc h , B, 1986, 663. H.W.Bosch and B.B.Wayland, J. Oraanomet. Chem,, 1986, 317, C5. E.Delgado, J.Hein, J.C.Jeffery, A.L.Ratermann and F.G.A.Stone, J. Oraanomet. Chem,, 1986, Ipz, C23. E.Lindner and D.Goth, Chem. Ber, 1986, 119, 3859. U.Schubert and E.Kunz, J. Ornanomet. Chem., 1986, 303, C1. S.W.Carr and B.L.Shaw, I. Chem. SOC.. Dalton Trans., 1986, 1815. R.T.Edidin and J.R.Norton, J. Am. Chem. SOC., 1986, 108, 948. R.Horlein and W.A.Herrmann, J. Oreanornet. Chem., 1986, m, C38. H.Werner and H.Otto, Chem. Ber., 1986, 119, 3866. A.B.Antonova, S.V.Kovalenko, N.A.Deikhina, E.D.Korniets, P.V.Petrovskii and A.A.Ioganson, Bull. Acad. Sci. USSR, Div. Chem. Sci,. 1985, B, 2624. W.Bernhardt and H.Vahrenkamp, Oraanometallics, 1986, 2, 2388. (a) R.Blumhofer and H.Vahrenkamp, Chem. Ber., 1986, Ilq, 683; (b) D.Mani and H.Vahrenkamp, w, p.3639. S.S.D.Brown, P.J.McCarthy and I.D.Salter, J. Oraanomet. Chem., 1986, m, C27. K.Jonas, G.Koepe and C.Kruger, Angew Chem., Int. Ed, Enal., 1986, z, 923. O.Rossel1, MSeco and *I.Torra, J. Chem. SOC, Dalton Trans., 1986, 1011; P.Braunstein, O.Rossel1, M.Seco, I.Torra, X.Solans and C.Miravitlles, Ornanometallics, 1986, 5, 1 1 13. D.V.Khasnis, H.Le Bozec, P.H.Dixneuf and R.D.Adams, Oraanometallics, 1986, 5, 1772. E.Rosenberg, D.Ryckman, I.N.Hsu and R.W.Gellert, Inora. Chem,, 1986, a, 194. JMRagos ta and J.M.Burlitch, Qrnanometa l l i c~ 1986, 3, 1517. (a) H.J.Haupt, U.Florke and H.Preut, Acta Crvstalloar, Sect. C, 1986, Q, 665; (b) U.Florke. P.Balsaa and H.J.Haupt. ibid. p.275.

459 K.H.Whitmire, R.R.Ryan, H.J.Wasserman, T.A.Albright and S.K.Kang, J. Am. Chem.


Sot.. 1986, 6831. 460 J.Arnold, D.N.Shina, T.D.Tilley and A.M.Arif, OrPanometallic& 1986, 3, 2037. 461 J.S.Ricci, T.F.Koetzle, M.J.Fernandez, P.M.Maitlis and J.C.Green, J. 0 raanomet.

Chem, 1986, 383. 462 F.W.B.Einstein, R.K.Pomeroy and A.C.Willis, J3 Oraanomet. Chem,, 1986, 311, 257. 463 L.Parkanyi, C.Hernandez and K.H.Pannel1, J, Oraanomet. Chem, 1986, 301, 145. 464 C.H.Lin, C.Y.Lee and C.S.Liu, ,I. Am. Chem. SOC, , 1986, m, 1323. 465 K.H.Pannel1, J.Cervantes, C.Hernandez, J.Cassias and S.Vincenti, Qraanometallics,

1986, 5, 1056. 466 P.Jutzi, B.Hampe1, MB.Hursthouse and A.J.Howes, J. Oraanomet. Chem, 1986, m,

19; P.Jutzi and B.Hampe1, 1986, 301. 283. 467 P.B.Hitcock, M.F.Lappert, S.A.Thomas, A.J.Thorne, A.J.Carty and N.J.Taylor, L

Oraanomet. Chem., 1986, 27. 468 S.G.Anema, K.M.Mackay, L.C.McLeod, B.K.Nicholson and JMWhittaker, Anaew.

Chem., Int. Ed. Enal,, 1986, a, 759. 469 (a) T.M.Arkhireeva, B.M.Bulychev, A.N.Protsky, G.L.Soloveichik and V.K.Bel'sky,

J. Organornet. Chem, 1986, 317. 33; (b) V.K.Bel'sky, A.N.Protsky, B.M.Bulychev and G.L.Soloveichik, Dokl. Acad. Nauk SSSR, 1986, 287. 857.

470 M.Porchia, U.Cassellato, F.Ossola, G.Rossetto, PZanella and R.Graziani, J. Chem. &, Chem. Commun., 1986, 1034.

47 1 K.M.Kadish, C.Swistak, B.Boisselier-Cocolios, J.MBarbe and R-Guilard, Inora. Chem,, 1986, 22 4336.

472 H.Behrens, M.Moll, P.Merbach and K.H.Trummer, Z. Naturforsch, B, 1986, Q, 845; M. Moll, H.Behrens, P.Merbach, K.H.Trummer, G.Thiele and K.Wittmann, m, p.606.

473 V.Sriyunyongwat, R.Hani, T.A.Albright and R.Geanange1, Inora. Chim. Acta, 1986, m, 91. 474 N. Viswanathan, E.D.Morrison, G.L.Geoffroy, S.J.Geib and A.L.Rheingold, Inora.

Chem,, 1986, a, 3100. 475 C.B.Lagrone, K.H.Whitmire, M.R.Churchil1 and J.C.Fettinger, Inora. Chem., 1986, 25,

2080. 476 M.R.Churchil1, J.C.Fettinger, K.H.Whitmire and C.B.Lagrone, I. Oraanomet. Chem.,

1986, 99. 477 K.H.Whitmire, C.B.Lagrone and A.L.Rheingold, Inora. Chem., 1986, a, 2472. 478 K.H.Whitmire, K.S.Raghuveer, M.R.Churchil1, J.C.Fettinger and R.F.See, J. Am.

479 K.H.Whitmire, T.A.Albright, S.K.Kang, MR.Churchil1 and J.C.Fettinger, Inora. Chem. SOC, 1986, U, 2778.

Chem., 1986, a, 2799.

10 Ligand Substitution Reactions of Metal and Organometal Carbonyls with Group V and VI Donor Ligands

1 Reviews BY D. A. EDWARDS

This y e a r has seen t h e p u b l i c a t i o n o f many reviews which f a l l w i t h i n t h e scope o f t h i s Chapter . Carbonyl complexes o f t h e Group IV1 and Group V2 metals and s u b s t i t u t e d ruthenium ca rbony l h a l i d e s 3 have been reviewed. s t u d i e s on d i n u c l e a r manganese ca rbony l compounds' and o f sono- chemical ly- induced l i g a n d s u b s t i t u t i o n r e a c t i o n s 5 have appeared. S e v e r a l reviews have been concerned w i t h p a r t i c u l a r t y p e s o f l i g a n d s 2 g . p y r a z o l e s and d e r i v a t i v e s 6 , t r i a z e n e s , t e t r a z e n e s and r e l a t e d compounds , 2 , 2 ' : 6 * , 2 " - t e r p y r i d i n e , * d i a z a d i e n e s and pyridine-2-carbaldehydeimines , phosphorus s u l p h i d e s and s imi la r cage molecules , lo c o o r d i n a t e d t r i f l a t e s and f l u o r o s u l p h a t e s , diphosphenes and t h e i r h e a v i e r homologues , l2 and phosphinidene , a r s i n i d e n e and s t i b i n i d e n e complexes. l3

e.g. t h i o n i t r o s y l , t h i a z y l h a l i d e s , s u l p h u r d i i m i n e s , s u l p h u r n i t r i d e s and t h i o n y l imide have been reviewed i n t h r e e ar t ic les . Over one hundred d i f f e r e n t fou r - , f i ve - , and six-membered i n o r g a n i c c h e l a t e r i n g systems form t h e s u b j e c t o f an e x t e n s i v e review.

Accounts of f l a s h p h o t o l y t i c 4

11

Sulphur-ni t rogen l i g a n d s

1 4

15

2 Papers o f Genera l I n t e r e s t

S u b s t i t u t i o n r e a c t i o n s of [Fe3 (CO) (p3-PPh) 21 can be induced

Reac t ions u s i n g P-donor l i g a n d s

(U3-PPh) 2 1 T i s a

by e l e c t r o n - t r a n s f e r c a t a l y s i s (ETC) under c o n d i t i o n s i n which the rma l r e a c t i o n s do n o t occur . t a k e p l a c e s e q u e n t i a l l y a t t h e t h r e e i r o n c e n t r e s . S u b s t i t u t i o n a l l a b i l i t y of t h e g e n e r a t e d r a d i c a l anion [Fe3 (CO)

key f e a t u r e . l6

Ph, M e ) u s i n g p o l y d e n t a t e phosphorus- and arsenic-donor l i g a n d s have a l s o been s t u d i e d and compared w i t h analogous the rma l r e a c t i o n s . l7

[Co4 (CO) [ C O ~ ( C O ) ~ ~ - ~ ( ~ . I ~ - P P ~ ) L I s p e c i e s (5 = 1 - 4 ) by s i n g l e s u b s t i t u t i o n

ETC-induced r e a c t i o n s o f [Co3 (CO) (p3-CR) I ( R *

E l e c t r o c a t a l y t i c and the rma l r e a c t i o n s o f (p4-PPh) 2 1 w i t h P (OMe) and v a r i o u s phosphines produce

2x

[For references see page 222 20 1


steps at separate cobalt centres. l8 substitution of a carbonyl ligand of a 2,3,1-diazaferrole tricarbonyl complex by P(OMeI3 or PPh3 has been achieved using electrochemical reduction conditions. l9

Electro-activated

2.1 Nitrogen Donor Ligands.- Metal carbonyl-diazabutadiene complexes continue to be studied. The complexes [M(C0)3(CNR) (R'N=CHCH=NR') 3 , (M = Cr, Mo, or W; Cy, or xylyl; their oxidation to 17-electron monocations and reduction to 19- electron radical anions explored. 2o between [Mo (CO) been studied. 21 [Ru (CO) 212{RN=C (R' ) C (R' 1 =NR} 1 complexes , (R = alkyl or aryl, R' =

HI Me), have been prepared. 22 ri2-CzI six-electron donor ligands in their Fe2 (CO) When these ligands are of the type RN=C(R')C(R")=NR"' with R' , R"

and/or R, R"'inequivalent, two isomers may be formed defined by which nitrogen atom is TI'- or v2-bonded. 23 [Fe2 (CO) (RN=CHCH=NR) I (R = Pril Cy) with HCECCO2Me lead to [Fe2 (CO) 5{RN=CHCHN (R) C ( 0 ) CH=CC02Me)l containing an 8-electron donor ligand, [Fe2(CO)6{RhCHCH=N(R)?HCC02Me}l containing a 6-electron donor heterocyclic ligand and [Fe2(C0)4{RNCHCHN(R)CHCC02Me}l containing a novel bis (v3-aza-allyl) ligand. 24 [MoZ (CO) (But-IAE) ] , [But-IAE is the 10-electron donor ButN=CHCH (NBut) CH (NBut) CH=NBut formed by two C-C coupled diazabutadiene ligands], results in Mo-Mo bond cleavage and uncoupling of B ~ ~ - I A E to give [ M O ~ (CO) (B~~N=CHCH=NB~~) 2 ~ .

tetramethylbiimidazolate complexes of Mn(1) and CpMo(I1) have been prepared in which the anions act as bidentate chelate ligands.26 containing a-amino acid anions have been characterised. Some [M(CO) 5(amino acid ester) I isolated.

t R = Me, Pri, Bu , R' = Pril But, Cy, or E-tol) have been isolated and

The kinetics of the reactions (py) 2 1 and PhN=C (Me) C (Me)=NPh, phen, or bipy have Thermally inert , but photolabile

Diazabutadienes act as rll-EI c ~ ~ - N ' , complexes.

Reactions of

Photolysis of

25

Anionic and neutral biimidazolate, bibenzimidazolate, and

Many complexes of Cr(0) , Mo(0) , W ( 0 ) , Mn(1) and Re (I)

(M = Cr, W) complexes have also been 27

2.2 Phosphorus and the Heavier Group V Donor Ligands.- The bicyclic aminophosphorane Ph(H)b(OCH2CH2)2h reacts with [CpM(CO) 2X] [CpFe(C0)2L]X or [CpM(CO)L]X. tautomer PhP(OCH2CH2)2NH, which is either g-unidentate or

(M = Fe, X = C1, Br; M = Ru, X = C1) to give either The ligand L is the monocyclic

Reactions of Metal and Organometal Carbonyls 203

Fe (CO I 4

( 5 ) Me

Me Fe- /\

oc co


- P,N-bidentate . I n s o l u t i o n t h e c h e l a t e complexes a r e i n

e q u i l i b r i u m w i t h t h e i somer i c n e u t r a l s p e c i e s [CpM(CO)LX] , L

r e v e r t i n g t o a E -un iden ta t e bonding mode. A b s t r a c t i o n o f t h e

l i g a n d NH p ro ton of [CpM(CO)LlY ( Y = PF6, BPh4) l e a d s t o t h e f i r s t Fe and Ru phosphoranide complexes [CpM(CO) {v2-Phi) (OCH2CH2) 2fJ}] . The me ta l phosphoranides [CpM' (CO) 2{n2-R;' (OCH2CH2) 2k}] ( M I = Mo, W;

R = Ph, B z , v i n y l or a l ly11 a l s o have been i s o l a t e d . 2 8 phosphorane ( cyc len PHI, (1; n = 2 ) r e a c t s w i t h metal ca rbony l

dimers t o g i v e t h e dep ro tona ted 2,N-bonded phosphoranide s p e c i e s

tCo(C0) ( cyc lenP) 1 and [CpMo (CO) ( cyc lenP) I . 29 The cyclam-

phosphorane (1; n = 3) r e a c t s w i t h [Fe (NO) (CO) 2 1 , [Rh(CO) 2C11

and [CpM(CO) 3C11 (M = Mo, W ) t o produce t h e P-bonded l i g a n d

complexes [Fe (NO) (" = 1,2) and [CpM (CO) 2C1L] o r t h e

- P , N ( H ) - c h e l a t e complexes [Rh (CO) C 1 L l and [CpM (CO) 2 L l +. A l l

p roduc t s c o n t a i n t h e l i g a n d i n i ts t au tomer i c phosphine form ( 2 ) .

Deprotonat ion o f [CpM (CO) Ll + g i v e s t h e cyclamphosphoranide compounds tCpM (CO) (L-H) I .

Cyclen-

( C O ) 2-nLnl

230

Complexes c o n t a i n i n g P-bonded ( P r i 2 N ) 2PH,%. [M(CO) nLl ( M =

Fe, n = 4 ; M = C r , Mo, W , n = 51, cis-[W(CO)4L21 and [CPM~(CO)~LI

have been c h a r a c t e r i z e d . React ion of t h e s e p roduc t s w i t h HX

( X = C 1 , B r ) g i v e s t h e co r re spond ing (Pri2N)P(H)X complexes, wh i l e

[CpMn(CO) 2{Pri2NP(H)OMe}] and [CpMn(CO) 2{HP(OMe)2)] r e s u l t from

methano lys i s .

a f f o r d s complex ( 3 1 , a l s o o b t a i n a b l e from Na2Fe(CO) 4 , 1 .5 dioxane

and Pri2NPC12 i n e t h e r .

c a r r i e d o u t i n THF t h e nove l [Fe2(CO)6(Pri2NP)31 r e s u l t s i n which

t h e C=O group of ( 3 ) i s r e p l a c e d by a PNPriZ moiety.

between Na Fe (C0I4 , 1 .5 dioxane and E t NPC12in e t h e r i s more

complex, l e a d i n g t o (4) o r ( 5 ) . React ions of Mn2(CO)10 and

Co2 (CO)

[Co3 (CO) (p3-Pri2NP) ] , r e s p e c t i v e l y .

h e t e r o b i m e t a l l i c complexes have a l s o been i s o l a t e d e.g. i (p-PH (NPr 2) )MLnl , [MLn = C r (CO) 5 , M o (CO) , W (CO) I ?In (CO) ,CP] I

and metal-metal-bonded-[CpFe (CO) (p-CO) (p-PH (NPr12) )MLn-ll , [MLn,l = C r (CO) , W (CO) 4, Mn ( C O ) Cpl . 31

forming [Cp2Zr (p-PPh2) 2MLLl , [ML, = Mo (CO) , N i (CO) , S i m i l a r behav iour i s d i s p l a y e d b y t{n5-Ph2P (C H

r e a c t s w i t h Mo ( C O ) (nbd) t o g i v e [C12Zr{u-q5- (C5H4)PPh2I2-

M o (CO) 1 .

Dehydroch lo r ina t ion of [Fe (CO) 4{Pri2NP ( H ) C l ) ]

However, i f t h e l a t t e r r e a c t i o n i s

The r e a c t i o n

2 2

i w i t h (Pri2N) 2PH g i v e [Mn2 ( C O ) ( u - H ) {p- (P r 2N) 2P)1 and S e v e r a l r e l a t e d p-phosphido

[CpFe (CO) 2-

- -

The compound [Cp2Zr(PPh I a c t s a s a P , P ' - c h e l a t e l i g a n d , i n 32 P t (PPh3) 1

2 2

1 Z r C l 2 1 which 5 4 2

33


Further studies of metal-diphosphene, and -phosphinidene complexes and their heavier homologues have been reported. In [Cp2M02(CO)4(PhP=PPh)l a cis-diphosphene bridges the metal atoms generating the Mo2P2 core of a butterfly structure.34 The diphosphenes RP=PR are cs-g,a-g'-bonded to two metal atoms and n2-P=P- bonded to the third metal in [{M(C0)5}3(RP=PR)I (M = Cr, Mo, or W; R = alkyl, Cy, Ph, or anisyl). Some of the chromium compounds undergo formal [2+11 cycloadditions at the P=P double bond to give species containing cyclic ligands M. [(OC)5Cr{PhP(NR)PPh)Cr(CO)5] and [ (OC)5Cr(RPSPR)Cr(CO)51 (R = anisyl) .35 M(C0) L compounds (M = Cr, Mo, or W; RP=CHPh, RP=C=CPh2, RP=CPh2, or RP=C=PR; R = 2,4,6-But C H mesityl) have been prepared and their 31P n.m.r. features reported.36 affords both diphosphene [ (OC) M (RP=PR) M (CO) I and phosphinidene [ (OC) 5M(p-PR)M(CO) 51 complexes?37 Reaction of [Ph4Pl [HFe(CO) 4] with PhPC12 leads to [Fe(C0)4{PPh(H)C1}1, [{Fe(C0I4l2(PhP=PPh) I in which the diphosphene is cr-g-bonded to one iron but n2-P=P-bonded to the other, or to the first trimetallic diphosphine complex [PhqP] [ { (OC) 4Fe)2 (PhPPHPh) Fe (CO) 4] .38 Reaction of trans-RP=PR' , [R = (q5-C Me ) (C0I2Fe, R' = 2,4,6-Bu C H I with an excess of Fe2(C0)9 effects carbonylation of the diphosphene with cleavage of the P=P bond to give the P-metallated diphosphinomethanone (6) .39 electron fragment s. CpMn (CO) 2], caf; be converted into phosphinidene, diphosphine or diphosphene complexes on treatment with metallating agents. The preparation and reactivity of diphosphine and distibine complexes e PP (But) Me 1 I has been discussed. from the reactions of REXz (R = alkyl, aryl; X = halogen) with Na M (CO) (M = Cr, Mo, or W) . They are (i) 2 2 open, (no metal-metal bonds), [ (OC)5M(p-ER)M(CO) 1 (ii) closed (metal-metal bonded) valence tautomers [ (OC) 5M (p-ER) M (CO) 5] , and (iii) coordination.21 and [Cp (OC) Mo (p-PR' )Mo (CO) 2Cp] and the open complexes [{C~CO(CO))~(LI-PR')] and [{W(C0)5)2(p-SbR)I, [R = CH(SiMe3I2; R' = 2,4,6-But C H 3 have been characteri~ed.~~ of the phosphinidene clusters [M30s3 (CO) 17PR], [M20s3 (CO) 15PR] and [H2MOs3(C0)12PRI reactions of [HOs3 (CO) loPRH] with M3 (CO) 12. 43 Reaction of

1

n A wide range of

L = 0'-P-bonded - RP=PR,

3 6 2 5

or

Reduction of [M(CO) (PBr2R) 3 (M = Cr, W; R = menthyl)

5

t 5 5 3 6 2

Dihalophosphine complexes [MLn{P(R)X2)], [ML, = 16-

. meso- [{CpMn (CO) 2)2{l-I-Me (But) - Three types of products result

E = P, As, or Sb;

2

- 5 [{M(CO) }3ER] of type (ii) with additional E -+ M(C0)

The closed complexes [ (OC) 4Fe (p-SbR)Fe (CO) 41 1

2

Excellent yields 3 6 2

(M = Os, Ru; R = Ph, Cy) arise from


Na2Fe(C0)4,1.5dioxane with PC12R (R = 4-Me-2,6-But2C6H20) affords the unsymmetrically phosphinidene-bridged complex [ (OC)3Fe(p-PR)2- Fe (CO) 31 . 44 Four reaction types have been explored with the aim of producing iron-phosphorus cage compounds. Oxidation of [Fe (CO) [Fe2(C0)8] containing -PC1 moieties and [Fe(CO)4j were all explored, (R =

45 Me, Ph, or p-tol) . Some new compounds e.g. ( 7 ) were obtained. Among other P-donor ligand complexes reported are [CP(OC)~W=PR~I and [Cp(OC)2M=P(R')C(H)=PR'] (M = Mo, W; R = i-Pr, t-Bu; R' =

2,4, 6-ButC6H2) , 46 the phospha- and arsa-alkenyl complexes I(q5-C Me )Fe(CO)2(n1-P=CRR')1 (R = R' = SiMe3; Ph, mesityl, or But), [ ( q -C5Me5)M(CO) (T~'-P=CRR')] (M = Ru, 0 s ;

(PHR) 2 1 , photolysis of [Fe2 (CO)

2-

(PHR) 21 , reaction of 2 6 2-

with RPC12 and reaction between iron complexes

R = OSiMe3, R' = 5 5 5

2 R = OSiMe - R' = Ph, mesityl) , [CpMo(CO)2{TlL-P=C(SiMe ) 11 and [CpFe(CO) 2{n1-As=C(OSiMe3)R}] (R = But, mesityl, or 2,4,6-But 3 - C H ) . 6 2

3 ' 3 2

47

2 . 3 Group VI Donor Ligands.- The triflate complexes [CpM(CO) - (PR3) (OS02CF3) ] and [ (r15-C5Me5)M' (CO)L(OS02CF3) I (M = Mo, W; M' = Fe, Ru; L = CO, PMe arise from reactions of ICpM(C012- (PR3)X] or [ (q5-C5Me5)MI (CO) (L)X] with ROS02CF3 (X = H, C1, or

Me; allow the preparation of the unidentate perrhenato-complexes [LnM(ORe03)1, [LnM = Re(C0I5, Rh(C0) (PPh 1 2 , Ir(C0) (PPh3I2, OsTCO) (PPh3) 3H, or Ir (CO) (PPh3) (H) Cl] . " Routes to the sulphur monoxide complexes [Fe(CO)2{P(OPh)3)2(SO)l, [{Mn(C0)4(PPh3J)2- (u-SO) I , [ {CpMn (CO) 1 (u-SO) 1 , and [Fe3 (CO) (u3-S) (v3-SO) I have been established.502 :he thioxophosphines RPS (R = Me, Et, Ph, or 4-XC6H4; X = MeO, Me, or F) are stabilized in [C~MO(CO)~(O,~~- RPS)MO(CO)~C~] and [ (OC)5Mn(cr,~2-RPS)Mn(CO)41. 51

2

3

R = H, Me, or SiMe3) .48 Halide-perrhenate exchange reactions

3 Groups IV and V

Reaction of Cp Ti(CO), with S N

2 2

produces two heterocyclic

species, [ Cp ?iN=S=kN=S=h] and [Cp TiSSN=S=N] . 52 Reactions of Cp2Ti(C0)2 with purine and adenine occur in an oxidative manner. Kinetic studies indicate that reactions of (n5-Cp*)Ti (CO) C5H5, C5Me5 or C H ) with phosphines or phosphites occur by a dissociative mechanism. Analogous reactions of ( n -Cp*)M(CO) (M = Zr, Hf) involve associative mechanisms. 54 and structure of [Cp2Zr (CO) {P (OMe) ,I] has been reported.

4e-----( 5 3

(Cp* =

5 9 7 2

The preparation 5 5


The anions [M(C0I61- (M = Nb, Ta) can be oxidised to seven- coordinate [M (CO) (THF) (acac) I and subsequent reactions lead to [M(C0)3(acac)L21 (L = PPh3, CyNC; L2 = dppe) and [Nb2(~-X)3(CO)81- (X = 02CMe, OMe, or C1) . 5 6 The complexes [HM(COIn (phosphine) ] have been prepared by treating [Et Nl [M(CO) n+l (phrsphine) ] with silica gel, or by photolysis of [HM(CO)n+l(~hosphine)I, [M = V or Nb, = 2; M = Nb or Ta, n = 3 ; phospgine = PhP(CH2CH2PPh2)2, P (CH2CH2PPh2)

' {C H NCH=NCH (Ph) Me 1 ] chelates have been prepared from CpV (CO) In contrast to the rapid associative kinetic behaviour of Cp V(C0) 2 and (q5-C Me 1 V(C0) in carbonyl substitution reactions, (n5-C 5 7 2 H ) V(CO), C~(~I~-C~H,)V(CO) and Cp(q5-2,4-Me2-pentadienyl)- V(C0) react slowly, a dissociative pathway dominating over a ligand-dependent pathway.

4

or {Ph2PCH2CH2P (Ph)CH - 1 1 57 2 2 Diastereomers of [CpV(CO) 2{NH2CH2CH (Me)NH2)1 and [CpV(CO) -

258 4' 5 4

5 5 2

59

4 Group VI

4.1 presented for formation of [M(CO) (r11-L2) I immediately following photolysis of M(C0) -potentially bidentate nitrogen donor ligand mixtures. Using ligands such as bipy, phen, diazabutadienes, 2-pyridinal-imines and their derivatives, extrusion of a carbonyl ligand follows to give IM(COI4L21 chelates. [M (CO) (q1-L2) ] complexes can be isolated where L2 = di (2-pyridyl) - methane and -ethane. 6o The preparation and electronic spectra of many nitrogen donor ligand complexes have been reported, solvato- chromism and the nature of the charge transfer bands being of prime consideration. Ligands employed include pyridine, bipy, phen and their derivatives, pyrazine, 2,2'-bipyrazine, 2,2'- and 4,4'-bipyrimidine, 3,3'-bipyridazine, azo-2,2'-bipyridine, 2,5-bis(2-pyridyl)pyrazine and 3,6-bis(2-pyridyl)-l,2,4,5-tetra- zine. 61 of some of the above ligands has been published.62

Carbonyl Complexes of Cr', Moo, and Wo.--Evidence has been

5

6

However, stable

An e. s . r . study of complexes containing anion radicals

Hydrazine and diazene complexes [M (CO) (RNHNHR' 1 1 I [M (CO) 5- 5 (trans-RN=NR')] and [M(C0)5(Cis-RN=NR')] have been synthesised (M = Cr, W; diazene complexes consist of a mixture of isomers with the metal coordinated preferentially at the nitrogen bearing the smaller R group.63

R = Me, Et; R' = Et, Prl). The hydrazine and trans-

The complexes [M(CO) 3(bipy) (nl-dipyam) 1 (M = Mo, W) ,


R R

R R

( 7 ; R=Me,Ph , p-tol)

Me I

Q \.!4

Reactions of Metal and Organornetal Carbonyls 209

[M(C0)3(dipyam)Ll and [M2(C0)6(di~~am)31 have been characterised. 64

6 phthalaldehyde using [Mo(CO) (TI -C H Me) I as template gives complex (8) .65 The anion [Mo(CO) 3{HB(p~) 3}1- can be oxidised to the radical [Mo(CO) {HB(pz) 11' which may be decarbonylated affording the metal-metal triple bonded [Mo2 (CO) {HB(pz) 1 ] .66

4 3 2 Other nitrogen donor ligand complexes reported include some Cr (CO) 5-1H-isoindoles ,67 the arsa-aza-oxa-cryptand complex [Cr(CO)5{N(CH2CH2)3)8(As404)61 ,68 and [Mo~(CO)~L(DMF)~I, [L = tetrakis (2-benzimidazolyl) -1,2-ethanediamine] . 69

(M = Cr, Mo, or W; L = heterocyclic amine) (M = Cr, Mo, or W; 1 bridging dipyam)

Condensation of 1,2-diaminobenzene and

6 5

3 3

A considerable variety of Group VI metal carbonyl-phosphorus donor ligand complexes have been reported. Metal pentacarbonyl species characterized involve the 1

and Ph2PNSNPPh2, 71 PhCH2PCH (Ph) CHPh, 72 P (OR) (0Et)Me (R = H, Me, PrZiNCH2CH2) (SMeI2, 75 RILPX3-; = 1,2; R = -CH=CHR', -CH2-C(R')=CH2; R' =

77

E = 0 , n = 3-6) ,78 H, Ph; F2PE(CH ) EPF2 (E = S, 11 = 2-6; (R = alkyl, aryl, furfuryl) and Ph - P(tetrahydrofurfuryl)n (n =

1,2),79 (RE)BOCH2CMe CH d and (RE)80:H2CH2CH(Me)6 (E = NH,O, S; R = alkyl, aryl, SiM:3):80 Ph PC(S)NHR (R = Me, Ph),81 Ph2P(n6- Ph) Cr (CO) 3, 82 and 1-Ph P-2-Et NCH2-g-carbaborane.

Metal tetracarbonyl -g,P'-bonded chelate ligand complexes that have been isolated include those with R2P(CH212PR2 (R = m,- or 2-FC6H4, m-CF3C6H4) , 84 (Ph2P) 2NH, 70 PhN (PC12) 2, PhN{P (NHPh) 2)2, or the 1,3,2,4-diazadiphosphetidines {(PhNH)PNPhI3 and {(PhNH)PP- (NPh)2}2NPh,85 F2PE(CH ) EPF2 (E = 0 , n = 3-5; E = S, a = 2,3), 78

2L?t ligands and the adamantane-like complex (9) .86 The chelate complexes [M(CO) 4{Ph3-xP (tetrahydrofurfuryl) 1 involve p,g- bonded ligands,79 whereas [M(CO) 4{Ph2PC (S)NRTR")] R" = H, SiMe3) 81 and [M (CO) ( 1-Ph2P-2-MeSCH2-g-carbaborane) I contain P,g-bonded ligands. In the chelate complexes [M(C0)4- (RnPX3-n)], [Q = 1,2; R = -CH=CHR', -CH2-C(R')=CH2; R' = H, Ph; X 2 Cl,-Br, or NEt21, the alkenylphosphines are both p- and q2-C=C-bonded. Similarly, the furfurylphosphines Ph2P (CH2C4H30) and RP(CH2C4H30)2 (R = alkyl, aryl, furfuryl) form W(CO)$ complexes in which the furfurylphosphines are bonded y& a-g- and n2-furyl ring interactions.

X = C1, Br, or NEt I ,76 Ph P{P(O) (OEt)21n (n = 1-3), 2 3-a

RP(furfury1) 2 2

83 2 2 2

(R' = Me, Ph; 8 3

79

Unidentate P-bonded ligand-*tal tetracarbonyls studied


include [Mo (CO) (Ph2PNHR) (Ph2PF) I (R = H, Me) , 87 [Mo (CO) qIPh2PP- ( 0 ) (OEt)b)21 , and [M(CO) (PCy2H) 21. The latter can be converted into the metal-metal bonded species [(OC)4M(p-PCy 1 MI- (PPh3)] (M = Mo, W; Some metal tricarbonyl and dicarbonyl-phosphine complexes have been characterised - viz. [Mo (CO) 3{P (NHPri) 3 l 3 l , 89 [M (CO) 3{MeGe (OCH2PMe2) 1 I and [M (CO) {MeSi (OCH2PMe 1 (CH2CH2PMe2) 3-n} I ( 2 = 0-2) , [Mo (CO) 2- {Ph2P(CH PPh2j21 ( & = 1 - 3 ) ,gl [Mo(C~)~(CNR),(PR'~),] (R,R' =

alkyl or aryl) including a study of their electrochemical and chemical ~xidation,'~ and isomers of [Mo(CO) ( r l -SO2) (triphos) I , [triphos = MeC (CH2PPh2) 3 , PhP (CH2CH2PR2) 2;

77 - 2 2

M' = Ni, Pd, or Pt). 88

2 5 2n

1

R = Ph, p-toll , [Mo (CO) (PIX3) (r11-S02) 1 and [Mo (CO) (PR3) (r12-S02) 1 . 9 3

A number of new poly- and ambi-dentate phosphines have been prepared and reactions with Group VI metal carbonyls described. Thus, [Mo(CO) membered rings and [(Ph P) CHCH212PPh is pentadentate in 2 2 [ (OC) 3$o{ (Ph P) CHCH26 (Ph) CH2CH (PPh2) 2)W (CO) 41 . 94 derivative [?q5fPh PC H ) Co] , L2, acts as a bridging ligand in [{Mo(CO) 1 (u-L ) I and as a chelate ligand in [Mo(CO) 4L21 and its mono-cation. 95 Both Ph2PCH2CH2CN and Ph2PCH2CH(Me)CN react with W(CO)6 and NaBH4 in alcohols to give mixtures of phosphine-imidate complexes [W(CO) {Ph2PCH2CH (R) C (OR') NH]] and phosphine-amine complexes [W(CO)4{Ph2PCH2CH(R)CH2NH2}l Reactions of EPh3 (E = P, As, or Sb), PEt3 or P(OMeI3 with the

1 2 phosphinothioformamide chelate complexes [M(C0)4{Ph2PC(S)NR R 11 (R1 = Me, Ph; R2 = H, Me) proceed -- cis/trans-mixtures of [M(CO) 4L{q1-Ph2PC (S)NR R 11 .

cyclohexaarsine in a previously unknown twisted boat conformation. In the presence of oxygen, Mo(CO)~ reacts with cyclo-(MeAs)5 to give the first metal complex of an alkylarsaoxane, [(Mo(CO)~)~- { cyclo- (MeAsO)

(Ph PI CHCH2PPhZ]I contains one four- and two five-

The cobaltocene

3 2 2

2 5 4 2 5 2

4 (R = H, Me; R' = Et, Prn)?6

with M-S bond cleavage to give 1 2 9 7

The complex [Mo(CO) c clo (P~AS)~] contains a 1,4-bidentate 4 y - 9 8

] , which contains a 12-membered As606 ring. 99

Reaction of [(Ph P) N]C1 with NaOMe affords the novel 3 2 compound Ph2P(0)NPPh3. (NPPh3) 11 on reaction with [W (CO) (THF) I -loo . metal carbonyl-sulphur donor ligand complexes that have been reported are [W(CO)5{S(MR3)R')] and [W(C0)4(p-SR')]2 (M = C, Si,

101 Ge, or Sn; [w (co) 5L] , [L = pyridinium-2-thiolatef lo2 and 6N(SiMe3)B(Me)N(H)B(Me)h(SiMe3)103] , [(Cr(C0)5)2(p-ER2)1 , [E = s,

This gives the 0-bonded [W(CO) 5 io = PPh2- Among the Group VI

R = Me, aryl; R' = CSH4X; X = MeO, C1, CF3),

Reactions of Metal and Organometal Carbonyls 21 1

Se, or Te; (u-SCH2C02Et) 21 and [Mo2 (CO) (NCMe) (y-SCH2C02Et) 2 1 , 2105 and [Mo(CO)~L~I , [L3 = MeS(CH2)2S(CH2)2SMel .lo6 studies of [W(CO) 5 W(C0l5 unit is stereochemically rigid while tungsten-sulphur 1,2- metallotropic shifts take place. lo7 [Cr (CO) (1,3-benzodithiole) 1 have been reported. lo8 The reaction of [Mo(CO) (NCMe) 31 with [Et4Nl [Fe6S6Cl61 gives [Et Nl [{Mo (CO) 3 } 2 - Fe S C1 1 and, remarkably, the analogous Ph4P+ salt can be 6 6 6 obtained using [Ph4P12[Fe4S4C141. The anion, which has each Mo(C0l3 unit bonded to three sulphur atoms of the Fe5S5C16 core has possible relevance to the Fe/Mo/S centre in nitrogenase. related [Et4Nl characterized. log

R = Me, R2 = (CH213, (CH2)41,104 [Et N1 [Mo~(CO)~-

Dynamic n.m.r. (PhCH2SSCH2Ph)l show that the square pyramidal

The stereodynamics of

4 4

The {W (CO) l 2 Fe6S6 (E-MeC6H40) 6l has also been

The kinetics and mechanisms of (i) the displacement of chelating ligands from [Cr (CO) 4L21 by phosphines and phosphites, [L2 = 4-Me-1,2-(MeSI2C6H3, Me2N(CH2) 3NMe21, the a-P,q2-C=C-chelate complex cis- [W (CO) 4{Ph2P (CH2) 3CH=CH2)] from cis- [W(CO) (C H NH) { r l -Ph2P (CH2) 3CH=CH2)1 , (iii) substitution reactions of cis- [Cr (CO) (RSCH2CH2SR) ] (R = Et, Bu ) with P (OEt) 3, and (iv) carbonyl ligand displacement from [ (OC) 4Mo (u-PEt2) 2- Mo (CO) 4] by phosphorus donor ligands, have been explored. 1l0

(ii) the formation of

1 t 4 5 10 -

4.2 Carbonyl Complexes of Mo" and WI1.- Reactions of Mo I (CO) 2 4 8 with ligands lead to mononuclear seven-coordinate [MoI~(CO)~L~] [L = THF, py, PMe2Ph, PEt2Ph; L2 = dmpm, dppm), [MoI~(CO)~- (nl-dmpm) (q2-dmpm) I and [Mo12 (CO) (n2-dmpm) 21 or by using more forcing reaction conditions the metal-metal quadruply bonded [Mo I L I The capped trigonal prismatic cation [Mo (CO) C1 (dmpe) 1' arises from the reaction of MoC12(C0)4 with dmpe. [M12(C0)3(NCMe)2] (M = Mo, W) with ligands have been described in a profusion of brief notes. Among the seven-coordinate products are [M12(C013L21, [L = py, P(OMeI3, P(OPhI3; phen, (n5-Ph2PC,H4) 2Fel, [MI2 (CO) (EPh3)Ll, [L = MeCN, P (OPh) 3,

E = P, As, Sb], [MI(C0)3(EPh3) (S2CNEt2)1 and [M12(CO)L2-

(L = PMe3, PMe2Ph, PEt2Ph; L2 = dmpm, dppm) .ll1

2 The reactions of

2 4 4

L2 = dppe, bipy,

[L = MeCN, PPh3, P(OMeI3; L2 = dppe; R = Me, Phl . Seven-coordinate carboxylato- and thiocarboxylato- complexes that have been described include [Mo (CO) (PPh3) 2Br (EOCR) ]

[Mo (CO) (PPh3) (EOCR) 2I IMO (CO) (PPh3) (SOCR) 2I I [MO (CO) (PEt3) 2-


1 1 4 (02CCF3) 21 and [Mo(CO) 2{P (OMe) 3 1 { ~ - (0 )P (OMe) 2) (02CCF3) 1 2. React ions o f [M(CO)3(PR3)2X2]

a p p r o p r i a t e sodium s a l t a f f o r d t h e c h e l a t e complexes [M(CO12(PR312-

(L2)Y] (L2 = a c a c , h f a c a c , t r o p o l o n a t e , 02CH;

The formate l i g a n d s of [Mo (CO) u n i d e n t a t e and b i d e n t a t e c o o r d i n a t i o n modes i n s o l u t i o n .

2 t h i o l a t o - a n i o n s g i v e p roduc t s such as [Mo (CO) (SC6H2Pri3) 3 1 - and

[Mo(CO) (SC6H3Ph2) 2 1 . t h e l a t t e r has one t h i o l a t o - l i g a n d 5-bonded b u t t h e o t h e r bo th 5- and r16-Ph bonded. '16 [ W ( C O ) B r {P(OMe) 3]2{Me2AsC(CF3)=C(CF )AsMe2)1 has been c h a r a c t e r -

i s e d . 1172 A r ange of seven-coordinate [M(CO)

(2 = 1,2; ( X = h a l i d e ) bis(pyrro1e-N-carbodithioate) c h e l a t e complexes have

been p repa red . The 16 -e l ec t ron fragment [M(CO) (S2CNC4H4) 21 appea r s t o b e more e l e c t r o p h i l i c t h a n [M(CO)2(S2CNEt2)2], t h e

l a t t e r a l s o forming many seven-coord ina te adduc t s . 118

( R = E t , Ph; X = C 1 , B r ) w i t h t h e

Y = C 1 , B r , 0 2 C H ) .

( P E t 3 ) ( 0 2 C H ) 2 l r a p i d l y exchange

The r e a c t i o n s between MoBr (C0lq and s t e r i c a l l y h inde red

The former is t r i g o n a l b ipy ramida l wh i l e

The capped t r i g o n a l p r i s m a t i c complex

3 L (S2CNC4H412] 3-n n

L = u n i d e n t a t e n e u t r a l donor) and [M(C0l2X(S2CNC H 1 I - 4 4 2

S t a r t i n g from cis- [Mo (CO) ( b i p y ) (NCMe) ] [BF4] r o u t e s t o a range o f s i x - and seven-coordinate Mo(I1) complexes have been

d e s c r i b e d . Complexes i s o l a t e d i n c l u d e s, t r a n s - [Mo (CO) (b ipy ) - (SBut) 2 1 , cis- [Mo (CO) ( b i p y ) X I ' (X = S 2 C N E t 2 - 3 N O 3 - ) , [No (CO) - (b ipy ) (ON01 I + , [Mo (CO) (b ipy ) 2Ll 2+ [L = PPh3, PBun3, o r P ( O h ) 3 l , and [ M o (CO) ( b i p y ) 2L2] 2+ [L = PEt3, P (OMe) 3] . I19

4.3 Cyc lopen tad ieny l , Arene, and o t h e r Complexes.- The p roduc t of

t h e r e a c t i o n between [CpCr (CO) 31 be [CpCr (CO) (PPh3) ]

(PPh3) 1 * . w i t h phosphines and p h o s p h i t e s have been s t u d i e d . 12' A mechanism

has been proposed f o r t h e p h o t o l y t i c r e a c t i o n o f [CpW(C0)3Mel w i t h

PPh3 i n i n e r t s o l v e n t s .

[CpW(CO) (PPh3)Mel. e f f e c t s d i s p r o p o r t i o n a t i o n t o [CpMo (CO) (PPh3) 1 and [CpMo(CO) 31-. This r e a c t i o n i s b o t h s o l v e n t - and wavelength-dependent.

Addit ion of phosphines t o metal-metal t r i p l y bonded [CpM(C0I2l2,

( M = Mo, W) , produces t h e adduc t s [CPM(CO)~(PHR R ) I , which on

h e a t i n g g e n e r a t e t h e phosphido-complexes [Cp M2 (CO) ( M = M o , W; R1 = R2 = H; M = Mo, R1 = M e , R* = H , M e ) . 124 The

complexes [CpCr (CO) 2{P (OR) 3 )E t ]

s u b s t i t u t i o n r e a c t i o n s o f [CpCr (CO) 3E t ] . 125

and PPh3, p r e v i o u s l y assumed t o

i s t h e monomeric r a d i c a l [CpCr (CO) 2-

S u b s t i t u t i o n r e a c t i o n s of t h e [CpW(CO) 1 ' r a d i c a l

The p roduc t s are [PPh3Mel [CpW(CO) 31 and

122 I r r a d i a t i o n of [CpMo(CO) 1 w i t h PPh3 +3

123

1 2 1 2

( u - H ) (u-PR R ) ]

( R = M e , Et) ar ise from

The p r e p a r a t i o n s and


optical activity of the enantiomers of the g,S-chelate complexes [CpM (CO) 2{Ph2PC (S) =NCH (Me) Ph) 1 (M = Mo, W) have been described. 126

6 Up to two carbonyl ligands of [ ( q -me~itylene)Cr(CO)~I can be replaced by P(OEtI3 in electrochemically-induced substitution reactions. phosphines generates [ (n-C6H6)CrlCO) 2Ll (L = Ph2PMe, nl-dppm). 127

The kinetics and mechanism of reactions of several [(q-arene)- Cr(C0)2(CE)I complexes with P(OR13 (E = S, Se; R = Me, Ph, Bun, or Cy) have been studied. The reactions are first order in both substrate and P (OR) {P (OR) 3}31 . 128 The cycloheptatrienyl complexes [WI (CO) 2L2 (v3- C7H7) 1 , (L2 = dppm, dppe) , [W(CO)2(n -dppm) (r17-C7H7) I + and [W (CO) (rl -dppm) (q7-C7H7) I' may be prepared from [WI (CO) (q7-

Photolysis of [(~I-C~H~)C~(CO)~I in the presence of the

and lead eventually to E- [Cr (CO) (CE) - 1

2 129 C7H7) I .

3 Ally1 complexes [Mo(CO) 2X(L2) ( r l -C3H4R) 1, (L2 = phen, X = C1, NCS, R = 1-Ph; thiosemicarbazide or various thiosemicarbazones, X = C1, Br, or I; R = H, 2-Me) have been characterised.

L2 = 2MeCN, dppe, X = C1, R = 2-CH2C1; L2 =

130

5 Group VII

5.1 Carbonvl, Carbonvl Halide, and Related Complexes.-Reaction of Mn2(CO)10 with Cy2PH in toluene at llO°C does not cause metal- metal bond cleavage, the product being [Mn2 (CO), (p-H) (p-PCy2) (PCy2H) I The complex =,fac-[Mn (CO) (dmpm) 1 is the first example of a bis(dmpm) complex with a =,trans-arrangement of the dmpm ligands. Along with the mer,mer-isomer, it is ahproduct of the reaction of Mn2(CO)10 with dmpm. 132 [Mn2 (CO) [depe = Et2P (CH2) 2PEt2], arises from irradiation of Mn (CO) the presence of depe. 133 mixtures in CH C1 the tripod ligand is bidentate. 134 reaction of Mn2 (CO)

[M2 (CO) 8-2q (11-x) (ii-tedip) n1 , [Mn2 ((20) [Mna (CO) 10-2n (p-X) (p-tedi~)~]' (M = Mn, Re;

- N-donor solvents affords [Mn(CO13L3]+ and [Mn(COI5l-, (L = 8- or - 0-unidentate ligands). With many of these ligands a secondary disproportionation of [Mn(CO) 3L31' leads to [MnL61 2+ and

2 6 2

An equilibrium mixture of (depe) 21 and the monomeric radical [Mn (CO) (depe) I*, 3

- (Ph2PCH2) 3CMe 2 10 in

Photolysis of Re2 (CO) yields fac- [Re (CO) 3C1{ (Ph2PCH2) 3CMe)l in which 2 2

The major products of the with (EtO) 2POP (OEt) 2, tedip, are [Mn2 - Other tedip complexes studied include (p-tedip)n]. (co) 10-2n

X (p-tedip)nl , and 135 -

X = Br, I; 9 = 1,2). The photochemical disproportionation of Mn2(CO)10 in 0- or


[Mn (CO) 51- . l i g a n d s , b u t does w i t h m u l t i d e n t a t e l i g a n d s 5 dmpe, t r i p h o s , and t e t r aphos . 13' ( R = Ph, Me, o r CF3) i n i t i a l l y y i e l d [Mn(C0I5(SR)I s p e c i e s which

e a s i l y l o s e carbon monoxide t o l e a v e mix tu res o f [Mn2 (p-SR)

and [ (Ph3P) 2 N l [Mn2 (P-SR) (CO) 61 .

M e N 0 , 2 H 0 i n s o l v e n t s o f low donor a b i l i t y t o g i v e [Re3(p-H)4-

(CO) g L l - (L = M e N , M e 3 N O ) and t h e nove l hydrogen-bonded adduct

[Re3 (p-H) (CO) (p3-O--H--NMe3) I - . Reac t ions o f [Re3 (p-H) (CO)

w i t h M e C N , PPh3, o r py occur by s e l e c t i v e s u b s t i t u t i o n of an a x i a l CO l i g a n d o f t h e R e ( C O I 4 v e r t e x t o g i v e u n s a t u r a t e d [ R e 3 ( p - H I 4 -

( C O ) 9 L l - an ions .

t o s a t u r a t e d [Re3 ( u - H )

l i g a n d s .

D i s p r o p o r t i o n a t i o n does n o t occur w i t h P -un iden ta t e

Reac t ions of [ (Ph3P) 2Nl [Mn (CO) 5 1 w i t h R2S2

(CO) 8 l 137

The u n s a t u r a t e d c l u s t e r anion [Re3(p-H)4(CO)101- r e a c t s w i t h

3 2

3

An a l t e r n a t i v e r e a c t i o n w i t h phosphines l e a d s

(CO) 10(PR ) 1 - an ions by loss of two hydr ide

The s y n t h e s i s of s e v e r a l Re (1 ) -n i t rogen donor l i g a n d complexes

3 2 13 8

have been r e p o r t e d and t h e emis s ive n a t u r e o f t h e i r me ta l - l i gand

charge t r a n s f e r e x c i t e d s t a t e s d i s c u s s e d . Examples i n c l u d e

[Re(C0)3C1L21 (L2 = b ipy , phen and t h e i r d e r i v a t i v e s , 2,2'-

b i p y r a z i n e , or 2 , 2 ' - b i p y r i m i d i n e ) , [{Re(CO)3Cl)2(p-2,2 ' -

b ipy r imid ine ) ] and [ ( b i p y ) 2Ru (p-2,2 I -bipyrimidine) R e (CO) 3C1]- React ion of R e (CO) B r w i t h 1 , 4 , 7-tr iazacyclononane, [PF612. 5

L3 , a f f o r d s t h e a i r - s t a b l e [Re (CO) 3L3 1 B r . l4O A range of cyano- and thiocyanato-Mn(1) ca rbony l complexes e .g . c i s , c i s o r c i s , t r a n s -

[Mn(CO)2X(L2){P(OPh)33] , fac-[Mn(C0)3XL2] and fac-[{Nn(CO)3L2}2-

( u - X ) 1 + ( X = CN, SCN;

p repa red . w i th Ph2PSiMe3 a r e s e n s i t i v e t o r e a c t i o n c o n d i t i o n s .

- cis-[M(CO) 4X(Ph2PSiMe3)] , cis-[M(CO)4X(Ph2PH)] and [M2(CO)

(p-PPh2) 1 . 142 ( an ion = v a r i o u s b i d e n t a t e amido, c a r b o x y l a t o o r t h i a z o l a t o groups) have been p repa red from [Tc (CO) 3 C 1 (PPh3) 2 ] . l4 complexes [Re (CO) ( d i k e t ) 3 , [Re (CO) (CNR) ( d i k e t ) 1 , and [Re (CO) 2-

(CNR),(diket)] R = But, x y l y l )

have been c h a r a c t e r i s e d .

13'

- - - -- L2 = b i p y , phen, o r dppm) have been

Reac t ions o f M(C0) X ( M = Mn, R e ; X = C 1 , B r , o r I ) 5 Produc t s a r e

( u - X ) -

The Tc ( I ) complexes [Tc (CO) (PPh3) ( an ion ) I ,

The B-diketonate

( d i k e t = acac , t f a c a c , o r h facac ; 144

5.2 Cyc lopen tad ieny l and Arene Complexes.-The e l e c t r o n i c

s t r u c t u r e s and e l e c t r o n - t r a n s f e r behaviour of [{Cp*Mn(CO) 3 (p-

o r n5-C M e ) have been s t u d i e d by e l e c t r o n i c spec t roscopy , c y c l i c

py raz ine ) 1 and [Cp*Mn (CO) (q 1 -pyraz ine ) 1 (Cp* = n5-C5H5, i51C5H4Me,

5 5


voltammetry and the e.s.r. spectra of their anion radicals. The systems I{ (q5-C5H4Me)Mn(CO) 2)2 (P-L) 1 [ L = RO-, imidazolate, or R'C(CN12 ; characterised by e. s .r. spectroscopy as spin-delocalised Mn'Mn'' systems. 145 Benzyl azide reacts with (q5-C H Me)Mn(CO) (THF)] 5 4 2 to yield (10) which is photoactive, producing PhCH2NC0 or PhCH2- NHC(0)OMe when irradiated in THF or MeOH, respectively. 146 The reaction of [CpMn (CO) 2{P (=NSiMe )N (SiMe3) 2l with Re (CO) 5Br yields (11) which contains a 6-electron donor mono-phosphorus analogue of a triazenido anion. 14'

- R = t-Bu or adamantyl; R' = t-Bu or HI have been

3

Other compounds studied include [ (n5-C5H4Me) Mn (CO) { (Ph2PC5H4) 2Fe) 1 , [CpMn (CO) ( r l 1 -dppa) I , and [ {CpMn (CO) 2)2 (U-L) ] , [L = dppa, S=C=CBuc2, orpER2, E = S, Se, Te; P, = He, ( c H ~ ) ~ , ( c A ~ ) ~ I . ~ ~ ~ , ~ ~ ~ In [C~M~(CO)~LI (L = rll-diop, r l l -

norphos) the potentially chelating optically active phosphines are unidentate. These complexes may be used as catalysts in enantioselective hydrogenations or hydrosilylations.

[ ( q -arene)Mn(C0)3]+ have been studied. I (~~'-arene)Mn(CO)~(PR~)l+ (arene = C6Me6, C6HMe5;

149

Some Me NO-initiated carbonyl substitution reactions of 3 6 Products are of the type R = Ph, OMe). 150

6 Group VIII : Iron, Ruthenium, and Osmium

6.1 Iron, Ruthenium, and Osmium Carbonyl Complexes.- The rates of carbonyl substitution in [Fe(CO) 3L21+ radicals (L = phosphine) by a variety of pyridines have been studied electrochemically. After a substitution step, which occurs by an associative mechanism, the products disproportionate by an electron-transfer process to yield Fe(I1) and Fe(0) products. Stepwise carbonyl substitution from Fe(COJ5 by (CF 1 P in sunlight proceeds as far as 3 3 [Fe (CO) 2{P (CF3) 3)3] .152 (S2CNMe2) 2 l and [Fe(S2CNMe2) 2] from Fe2 (CO) been reported. 153 lysis of concentrated solutions of Ru3(C0112 under carbon monoxide, reacts with phosphines to form [RU(CO)~-~L~I species (5 = 1,2; L = PMe3, PMe2Ph). 154 Reactions of [M(CO) (H) C1 (PPh3) 31 with P (H) RPh lead to the formation of IM(C0) (HI C1 (PPh3) 2{P (H) RPh) J complexes (M = Ru, 0s; R = H, Ph). Further reactions of these products provide routes to [M(C0)2-nC1(PPh 1 L I [CIOql L = MeCN) , the phosphido-complexes TM(C0) 2C1 (PRPh) (PPh3) 21 and the phosphine complexes [ M ( C O ) 2{PR(OMe) Ph) (PPh3) 21 . 155 The chiral

High yield syntheses of [Fe (CO) 2 -

A new form of [RU(CO)~I~, prepared by photo- or Fe3 (CO) 12 have

(" = 0 , l ; 3 2 n


cations fac- [Ru (CO) (R) L (triphos) 1' have been synthesised from [Ru(CO) 2R(triphos) I + (R = alkyl;

reported e.g. [Ru (C0)Cl2 (NH3) 31 , [Ru(CO) 2C12 (bid) 1 (bid = e.g. en, 2,2'-biquinolyl, 1,2-diaminobenzene, 1,8-diaminonaphthalene, di (2-pyridyl) mine, di (2-pyridyl) ketone), [Ru (CO) X2L (bid) ] , [Ru (CO) L(bid)l+ and [Ru(CO)X2L(bid)l (X = C1, 02CMe; L = py, MeCN; bid =

bipy, phen) , the carbamoyl complexes [Ru (CO) 2X(C ( 0 ) N (Me) C5H4N)] (X = C1, acac) , and [Ru(CO)~L~I containing the quadridentate thiolato-amine ligands'SC6H4NHCH (R) CH (R)NHC6H4S- (R = H, Me) . 157 Hydrido-complexes characterized include [RuH (CO) L2 (PPh3) + (L =

pyridine and derivatives; L2 = bipy, phen), the thionitrosodi- methylamine complexes [MH(CO) C1 (PPh3) (PPh 1 1 (bidH = various 2-hydroxyphenones) , [MH (CO) C1 (PPri ) Ll

L = phosphine, isocyanide) . 156 Various Ru (11) and 0 s (11) carbonyl complexes have been

(NCMe) (bid) 1 2+, [Ru (CO) L (NCMe) (bid) I 2+, [Ru (CO) C1 (NCMe) -

(S=NNMe2) 1 , [RuH(CO) (bid) -

[L = 3 2 PMe3, P(OMel31, and [MH(CO)X(PPri3)2] (X = q 2 -02CMe, q 32:

acac) , [RuH(CO) 2 . ( S R ) (PPh3) 2l (SH)2(PPh3)21, and a variety of bidentate salicylaldimine Schiff base complexes, such as [MH(CO) (bid) (PPh3) 2l (bid = RN=CHC H 0-;

R = aryl, benzyl) .158 sulphonate complexes of Ru(I1) and OS(I1) have been prepared e.g. [M(CO) X(03SR) (H20) (PPh3) 21 and [M(CO) 2X(03SR) (PPh3) 2 l 03SR; R = Me, CF3). No n2-03SR complexes could be isolated, the complexes preferring to coordinate a water ligand.

(R = H, alkyl, or aryl) and [Ru(CO) 2-

6 4 A range of weakly-bonded unidentate

(X = C1,

Binuclear complexes are now reviewed. The pyridine-2- carbaldehyde imines, R-pyca, R'C H NC(R")=NR (R = alkyl, aryl; 5 3 R',R" = H, Me) react with Fe2(C0)9 and R U ~ ( C O ) ~ ~ to give [M2(C0)6- (R-pyca)] complexes containing six-electron donor (u-N, u2-N', 0 -C=N' ) ligands. Further reaction of [Ru2 (CO) (R-pyca) 1 gives [Ru2 (CO) (R-ape) ] species in which the 10-electron donor R-ape ligand, [R-ape = 1,2-bis(p-alkylamido)-l,2-bis~2-pyridyl)ethanel, consists of two C-C linked R-pyca ligands. 160 [Fe2(C0)9-2n(p-R2PCH PR 1 (; = 1,2; R = Me, Ph) undergo P-C bond cleavage on heating to give species containing p-R2PCH2 and p-PR moieties e.g. [Fe2 (CO) (p-R2PCI12) (p-PR2) I . However, pyrolysis of related complexes containing methyl-substituted diphosphines e.g. [Fe (CO) {u-Ph2PC(R) (R')PPh2)] (R,R' = H, Me) proceeds by loss of a phenyl group accompanied by 2-metallation of another producing [Fe2 (CO) 6{p-PhPC (R) (R') PPh (C6H4) 11. 16' [Fe (C0),(p-PR2)] radicals have been isolated (R = alkyl, Ph).

2

The complexes

2 2 2

2 -

2 7

Some air-stable 162

2


The reaction between Ru3(C0Il2 and e - P h PCH=CHPPh2, catalysed by

Facile elimination of Ru (CO) then leaves [Ru2 (CO) (U-Ph2PCH= CHPPh2)l in which the ligand is g,P'-chelating to one Ru and n2-C=C bonded to the other metal atom.163 diphosphazene-bridged complexes have been characterised, e.g. [M2 (CO) 5X(~-L2) 2l X, and [RU,(CO)~(U-X)~(P-L~)~I [M = Fe, Ru; X = halide; L2 =

(R0)2PN(Et)P(OR)2; with carboxylic acids give five types of products, (W-O2CR) 21 , [Ru2 (CO) (P-02CR) (H20) I I [Ru2 (CO) (P-02CR) (RC02H) 21 I

[Ru4 (CO) (u-02CR) (RC02H) 2 l , and [Ru (CO) (02CR) In, (R = aryl, Bus, or But). The distribution of products depends on the nature of R, the ratio of reactants and reaction conditions. 165 isomer of [Fe2(CO) of Fe3(C0Il2 with g-methyl-4-mercaptopiperidine. Despite the bulk of the ligand, infrared evidence shows the =-isomer can also exist.166

have been studied. Products isolated include [L (OC)

r k o ( C 0 ) 3], [" = 1,2; L = various phosphines zr P(OMe) 3; L = dppm], [ ~ P ( O M e ) 3 ~ 2 ~ 0 C ) 2 ~ ~ ( ~ - P P h 2 ~ ~ o ( C 0 ) 2 ~ P ( O M e ) 3 ~ l and [ (0Cl3- Rt(p-PPh2) (p-dppm) 80 ((20) 21 . 167

fragmentation reactions of M3(C0)12 proposed and should assist the rationalisation of available kinetic data. The key step is the ligand-independent heterolytic fission of a metal-metal bond to generate an open M3 chain containing one 16-electron unsaturated metal atom. 168 The kinetic data obtained for reactions of (a) Os3 (CO) 12 with 1-octene and with P (OEt) 3, [Os3 (CO) 12-n(NCMe) n] (c) the photosubstTtution and photofragmentation reactions of R U ~ ( C O ) ~ ~ and [Ru3(CO) 12-ELz1 be assessed in the light of the above mechanistic proposal. The reactions between R U ~ ( C O ) ~ ~ and a number of heterocyclic nitrogen donor ligands (- pyridine, pyrazoles, quinoline, 1,2,3,4-tetra- hydroquinoline, phenanthridine) have been explored. Cyclo- metallated products usually result, the common structural feature being the bonding of the nitrogen and the 2-carbon atom of the ligand and a bridging hydrogen to one edge of the Ru3 cluster. Pyrazoles, however, bridge one edge of the R u 3 cluster using both

2 (Ph P) Nl [O2CMe1, initially yields [Ru3 (CO) (U-Ph PCH=CHPPh2) 1 . 3 2 10 2

A number of types of

[M2 (CO)

R = Me, Pri, or Phl . 164 (P-X) (u-L2) 2l X, [Ru2 (CO) (V-X) X(p-L2) 21

12 Reactions of Ru3(CO) [RU~(CO)~-

The anti- (P-SC H NMel21 is the product of the reaction 6 5 9

Ligand substitution reactions of (OC) 46u (U-PPh2) do

n 4-5-

An alternative mechanism for carbonyl substitution and (M = Fe, Ru, 0s) has been

(b) (2 = 1,2) with - P- and =-donor ligands and

(" = 1,2; L = phosphine)16g can now


The Cp Fe (CO) 4-ca ta lysed s u b s t i t u t i o n 2 2 ' n i t r o g e n atoms.

r e a e t i o n s of M3(C0ll2 (M = Fe, Ru) and €l Ru (CO)12 is a u s e f u l 4 4 r o u t e t o p roduc t s such a s [M3(CO)12-2LGI

phosph i t e ) and [H Ru (C0)12,nLnl (g = 1 - 4 ) . 17'

b i d e n t a t e phosphine c o m p l e x e r F h a t have been r e p o r t e d a r e

[M3 (CO) l o ( ~ - L 2 ) I , [M = Ru, L2 = dmpm, dppee, sp ; dppm, dppee, sp ; dppee = (Ph2PI2C=CH2; s p = Ph P ( C H C H = C H 2 ) 1 ,

dppee) , [Ru3 (CO) (v-dppm) 3 l and [M3 (CO) (p-dppm) (nl-dppm) 1 (M = Ru, 0 s ) . 172

[M3 (CO) 12-nLn], S03-Na+ (H2E)T31 a s aqueous homogeneous c a t a l y s t s cons ide red . The s u l p h u r

d i imide S (NAsBut2) , L , a c t s a s an *-donor l i g a n d i n b o t h

17* H e t e r o c y c l i c t h i o - [ O s 3 (CO) l o ( ~ -L) 1 and [IOs3 (CO) 1112 ( P - L ) 1 . amides, HL, r e a c t w i t h [Os3 (CO) 10(NCMe) 21 t o g i v e [ O s 3 (CO) l o ( ~ - H ) -

( p - L ) ] p roduc t s i n which t h e thioamido l i g a n d s b r i d g e one edge o f an Os3 t r i a n g l e via t h e e x o s y c l i c s u l p h u r atom. 175 The novel t r i-

d e n t a t e sulphate-capped complex [H20s3 (CO)

t h e r e a c t i o n of [H30s3(C0)9(p3-CH)I w i t h 98% s u l p h u r i c a c i d .

analogous p3-hydrogen phosphate complex a l s o has been i s o l a t e d .

Routes t o t h e ruthenium ca rbony l c l u s t e r complexes [ R U ~ ( C O ) ~ ~ - ~ -

( u - H ) (pn-SBut) (u-dppm) 1 (" = 2,3) , and [Ru3 (CO) ( u - H ) (u3-S) (p-L2)] ( L = dppm, dpam, o r =-Ph2PCH=CHPPh2) have been

pub l i shed . 377 L i n e a r cha in [Os3 ( C O ) 12Br21 reacts w i t h PPh3 o r

PPh Me by s u b s t i t u t i o n and f r agmen ta t ion t o g i v e m i x t u r e s of

[Os3 (CO) 10Br2 (PR3) 2 1 , 10s (CO) (PR3) I and [ O s (CO) 2 B r 2 (PR3) 2 1 . The

complex [ O s 3 (CO) 10Br2 {P (OMe) 3}21 has been s t r u c t u r a l l y c h a r a c t e r -

i s e d . 178 produces [ O s 3 (CO) ( N M e 3 ) (U-H) (u-OH) (p3-S) ] which has an open cha in

of t h r e e m e t a l atoms, t h e non-bonded 0s----0s v e c t o r be ing spanned by t h e s u l p h i d o and hydroxo groups. 17' f o r ca rbony l l i g a n d s o f [ H R U C O ~ ( C O ) ~ ~ ] occur s p r e f e r e n t i a l l y a t Ru

whereas s u b s t i t u t i o n o f phosphines occur s e x c l u s i v e l y a t CO.

(2 = 1-3; L = phosphine, Among t h e 4 4

M = O s , L2 =

2 6 4 [M3(C0)8 (~-L2)21 (M = Ru, L2 = dmpm, dppee; M = Os, L2 = dppm,

The wa te r - so lub le metal c l u s t e r complexes

[IJ = 1-3, M = Ru; fi = 2, M = .OS; L = PiC6H4-fl- have been s y n t h e s i s e d and p o s s i b l e a p p l i c a t i o n s

1

( u -0 SO) ] a r i s e s from

The 9 3 3

176

2

The r e a c t i o n between [Os3 (CO) lo(p3-S) ] and Me3N0.2H20

S u b s t i t u t i o n o f amines

180

6 . 2 Cyclopentadienyl Complexes.-Time-resolved i n f r a r e d spec t ro - scopy has been used t o show t h a t [Cp2Fe2(p-C0)31 is t h e p r i n c i p a l

i n t e r m e d i a t e i n p h o t o s u b s t i t u t i o n r e a c t i o n s of Cp Fe ( C O ) 4 . T h i s 2 2 i n t e r m e d i a t e r e a c t s w i t h MeCN and phosphines t o g i v e [Cp2Fe2(C0)3L]

p roduc t s . 18' A wide range of complexes have been p repa red by


displacement of THF from ICpFe (CO) Cp2Fe2(C0I4 with AgC104 in the presence of ligands. Examples include (a) [CpFe (CO) 2Ll+, [L = 1,8-naphthyridine, pyridazine, 3,5-dimethylpyrazole, Ph3-,P(NR2In, (n = 0-3; R = Me, Et), Ph2PNHR (R = But, Ph), As(NMe2I3, ;'-RS(CH2),SR (n = 1,2; n1-1,4-dithiane, q1-1,3,5-trithiane, ql- (MeSI3CH, and R EX (R =

alkyl, Ph, NMe2; E = P, As, Sb; (L = Ph2PNHR; ligands) and (c) [{CpFe (CO) 2)2 (u-L2) 1 2+ (L2 = pyrazine and the - S-donors listed above acting as bridging ligands) . 182 between [CpFe(CO)2C1] and &-Ph2PCH=CHPPh L2, produces both [CpFe (CO) (q -L2) I + and [CpFe (CO) (n1-L2) 1 . of the chelate complex lead to [{CpFe (n2-L2) l2 (v-N2) I

(THF) I + or oxidation of

R = Et, Ph, Bz),

3 X = S, Sell, (b) [CpFe(CO)L21+

L2 = ?-donors listed above acting as chelate

Reaction

2 +2 Subsequent reactions 2+ , [CpFe-

(q2-L ) (N0)12+, [CpFe(n 2 -L2)L'lf (L' = NH3, HN3) and [CpFe(n2-L2)-

N ] .1 8 3 The thiolato-bridged complex [CpFe (CO) (v-SC5H9NMe) 3 3

results from the reaction of Cp2Fe2(C0)4 with 4-2-methylpiperidine disulphide. 184 [Me2SSMe][BF ] allow the preparation of the disulphide complexes 4 [CpFe (CO) L (PhSSMe) 1 [BF4] , P (OPh) 33. 185 Routes to the indenyl iron cations [ (q5-CgH7)Fe- (CO)2L]+, (L = CO, phosphines, phosphites, RCN, py) have been established. 186 [ (q5:q5-C5H4.C5H4)Ru2 (CO) 41 with a large excess of PMe3 yields trans- [Ru(CO) (PMe3) 21 and [ (v5-C5H4.C5H4) Ru ('20) (PMe ) 1 in which only one cyclopentadienyl ring is bonded to the metal.

Reactions employing the sulphonium reagent

[L = CO, PPh3, PPh2Me, PPh2 (OMe) , or

Reaction of the q5: n5-fulvalene complex

2187

7 Group VIII : Cobalt, Rhodium, and Iridium

7.1 complex [Co (CO) ( q2-Tj,g-TMPO) I results from the reaction of Co2 (CO) routes to the water-soluble complex [Co2 (CO) (amphos = Ph2PCH2CH2&Me3) have been reported and its value as an olefin hydroformylation catalyst assessed. 18' Other cobalt-

phosphine and -phosphite complexes investigated include [Co(CO) {P(OMe)3141+, [Co(CO) (TI -L2l21+ (L2 = dppm, dppe) , the chiral clusters [Co (CO) L ( v -CMe) (Ph PCH2PMe2)] phosphines e.g. MeP (0-anisyl) R; R = Ph, Cy] , [Co2 (CO) (L2) ] and [Co (CO) (L ) ] (solution structures and dynamics: L2 = dppm, dmpm, Ph2PCH2PMe2) , [{Co4 (CO) (v-dppe) 1 , [Co4 (CO) 10(dPPe) 1, and

Carbonyl Complexes.-The sixteen-electron planar Co(1)

with 2,2,6,6-tetramethylpiperidin-l-oxyl, (TMPO) . 188 TWO (amphos) 2 1 [PF6]

2

[L = CO or unsymmetrical 3 6 3 2 -

4 8 2 2


polymeric products e.g. (OC) llCo4{ (p-dppe) Co4 (CO) (p-dppe) - Co4 (CO) 111 . with PEt3 is [CoRh (CO) (PEt3) 21 , the Co-Rh bonded intermediates

- The final product of the reaction of Co2Rh2 (CO) 12

[Co2Rh2 (CO) (PEt 1 1 (" = 1,2) and ECoRh(C0) (PEt3) I also being isolable.

1gp.rr 3 II,

Complexes prepared fram [Rh (CO) 2C11 include (a) five-coord-

(bid = the anionic inate [Rh (CO) 2L2C11 (L = many imidazoles) , (b) [Rh (CO) (bid) I, [Rh(CO) {P (OPh) 3 l (bid) I and [Rh(CO) (PPh3) (bid) 1 chelate ligands, 2-carboxyquinolinato, l,l,l-trifluoro - 5,5,5-tri- methylpentanedionato, 2-hydroxy-N-nitrosobenzenaminato, oxinate derivatives, and the Schiff bases derived fran condensations of B-diketones with N-methyl-2-methyldithiocarbazates),(c) [{Rh(C0)2)2

- L ~ ] (d) [Rh(CO)L31, [L3 = tridentate pyrazolylgallate monoanions, X(Me)Ga(N C H (OCH C H N) ; X = Me, C11 , (el the metallacycles [tRh(CO) C1I2 (u-L2) , [L2 = trans-Ph2PCHCH2CHPPh2, Ph2PCH2As (Ph)- CH2PPh21 and (f) [Rh2 (u-Cl) (L2) 2l , [L2 = 1-CH2=C (Me)-2-Ph2P-g- carbaboranel . lg2 One member of a new class of liquid crystals containing a mesogenic organic ligand is *-[Rh(CO) ClL] CgH190C6H4C6H4CN) . lg3

4-~mino-3,5-bis (pyridin -2-yl) -1 , 2 , 4-triazole , (NH2bpt) , or its anion act as bidentate chelate ligands in the Rh(1) complexes [Rh(C0)2-II(PPh 1 (NH2bpt)l+ (a = 0, 1) and [Rh(CO) (PPh3) (NHbpt)1!94 Reaction of [Rh(CO)2C1]2 with Me2PCH2P(Me)CH2PMe2, dmmm, followed by addition of NaBPh4 yields [Rh2 (CO) in which a square-planar coordinated rhodium is bonded to an octahedrally coordinated rhodium a dative Rh-Rh bond. lg5 The complexes [Rh(CO)H (PCy3) 21 , [ R h 2 (CO) (u-CO) (PCy3) 3 1 and [Rh2 (CO) (u-CO) 2-

(PCy ) 3 can be interconverted using carbon monoxide and hydrogen. lg6 Reactions of [Rh(CO) (acac) ] with l13,2-oxazaphos- phorinanes XPO(CH2) 3NR, [R = HI alkyl; O(CH ) NR 1, give P-bonded complexes of the type [Rh(CO) (acacIL1. Trigonal bipyramidal [ R h (CO) (COMe) (SbPh3) 3] is the unexpected product of the reaction between [Rh(C0)2(dpd)l and SbPh3 in MeOH (dpd = 1,3-diphenyl-1,3-propandionato). lg8 (PCy3) 2], obtained by reaction of [Rh(CO) PCy3, the acac ligand is unidentate. lg9 with 2-pyridinethiol, (LH), which exists in tautomeric equilibrium with the thione form, leads to four types of product; [Rh(C0)3-n- C1 (LH) n] (" = 1,2) containing 5-bonded LH, [Rh112C12 (CO) (p -L) 2-

(L4 = tetradentate azine dianions e.g. -0C H CH=NN=CHC H 0-) , 6 4 6 4

I 2 3 3 2 5 4

(L = n- 2

3 ;

(p-dmmm) 2l [BPh41

- X = OEt, NMe2, NEt2,

19 7 2 3 2

In tRh(C0) (acacl- (acac) ] with excess

Reaction of [Rh (CO) 2C11

-

Reactions of Metal and Organometal Catbonyls 22 1

(LH) ] i n which LH i s i n t h e S-bonded th ione form and two p-L

anions span t h e metal-metal bond, and two products a r i s i n g by a i r

ox ida t ion , [RhlI1(L) (LH) 2 1 + and m x - [Rh (L) 3 1 . . phosphines and phosphi tes suggests t h a t t h e r e a c t i o n s involve an

a s s o c i a t i v e mechanism. 201 Reactions of [Et4Nl [ I r 4 (CO) l l B r l wi th

phosphines l e a d t o [Ir4(C0)12-nLlll (Q = 1 , 2 ; L = unidenta te

phosphines) , [Ir4 (CO) 11 (TI -L2) 1 and [ { I r 4 (CO) 11}2 (p-L2) 1 (L2 = dppp, dppb, trans-Ph2PCH=CHPPh2) , and [Ir4 (CO) loL21 c h e l a t e

complexes [L2 = Ph2P(CH ) PPh2 ( & = 1 - 4 ) , dmpe, c&-Ph2PCH=CHPPh2,

- 0- (Ph2PCH2) 2C6H41 . The s t r u c t u r e of [Ir4 (CO) 10(dmpe) 1 involves t h r e e br idging carbonyl l igands around a t r i a n g u l a r face of t h e

Ir te t rahedron.202

PCy H l ead t o t h e f i r s t t e t r a n u c l e a r i r id ium arsenido- and

phosphido-stabi l ized c l u s t e r s .

( P - A S B U ~ ~ ) ~ ] conta in ing a p l a n a r I r4 core with an i s o l a t e d Ir=Ir bond, and [Ir4 (CO)

1 2 core .

t o a f f o r d [Ir3 (CO) (p-PBut2) 3 1 , [M2 (CO) (PBut2H) (P-H) (P-pBut2) 1 (M = Rh, I r ) , and [Rh6 (CO) (P-CO) ( v - H ) (u-PBut2) 41 , t h e l a t t e r

having a novel Rh6 core c o n s i s t i n g of a Rh4 t e t rahedron br idged

on oppos i te s i d e s by two f u r t h e r Rh atoms.

2

I11 2 00

A s tudy of t h e k i n e t i c s of t h e r e a c t i o n s of I r4(C0)12 with

1

2 2

Reactions of Ir4 (CO) 12 wi th AsBut2H and 4 2

The products a r e [ I r4(C0)2(p-C0)2-

(p-CO) (p-PCy2) 41 conta in ing a t e t r a h e d r a l Ir4 The more s t e r i c a l l y demanding PBut2H reacts wi th M 4 (CO)

203

7.2

on r e a c t i o n wi th [ (q'-C5Me5) 2 C 0 2 (CO) 21 o r t (n5-C M e )Co (CO) 21 , t h e

products being [ (n5-C5Me5) 2 C 0 2 (CO) (As2S2) I , [ (n -C5Me5) 3C03-

(As2S4) I and [ (n5-C5Me5) 2 C 0 2 (As2S3) ] . As S

bridged by a su lphur atom. 204 have been prepared f r m [ C P R ~ ( C O ) ~ ] PR3 = P(OCH2)3CEt], and t h e i r p ro tona t ion s tudied .

complexes [Cp Rh (CO) (p-C0)Ll , 2 2 a l s o been i s o l a t e d . 205

s u b s t i t u t i o n r e a c t i o n s t o a f f o r d [ (q5-C Ph 1 Rh (C0)LJ complexes, [L = PPh3, AsPh3, P(OMeI3, P(0Ph) 3 1 . 2065 A5route t o t h e t r i p l y -

br idged dirhodium complexes [ (n5-C5Me5) Rh (p-pz) (p-CO) Rh ( L 2 ) I - [BPh4]

e s t a b l i s h e d .

Cyclopentadienyl Complexes.- Fragmentation of As4S4 occurs

55

The l a t t e r conta ins a novel

l igand a c t i n g a s a 4-electron donor with t w o n2-AsS u n i t s Eight [CpRh (CO) (PR3) I complexes

2 3

[ R = a l k y l , a r y l , OMe, OPh; I

The b inuc lear

[ L = P(0Ph) 3, P(OCH2)3CEtl have The pentaphenylcyclopentadienyl compound

(n5-C5Ph5) Rh (CO) 21 undergoes oxidat ively- induced carbonyl

(L2 = dppm, dppp, dppb, dpae, =-Ph2PCH=CHPPh2) has been 207

222 Organomerallic Chemistry

8 Group V I I I : N i c k e l , Pal ladium, and Plat inum

The p roduc t of t h e r e a c t i o n between N i ( C O I 4 and dmpm,

p r e v i o u s l y assumed t o b e t h e c h e l a t e complex [Ni(CO) (dmpm)], i s a c t u a l l y t h e dimer [ N i 2 (CO) (p-dmpm) J . 208

1-phosphaal lene complex, [Ni (CO) (r11-2,4 ,6-But C H P=C=CPh2) 1 h a s

been i s o l a t e d and s t r u c t u r a l l y c h a r a c t e r i s e d . 209

The r e a c t i o n s o f decanuc lea r pa l l ad ium ca rbony l c l u s t e r s e.g. [PdlO(CO) 14 (PBun3) 4 1 w i t h f u r t h e r p-, As-, or %-donor l i g a n d s can

l e a d t o e i t h e r s u b s t i t u t i o n p r o d u c t s e . g . [Pdlo(CO) 12 (PBun31 - (PPh ) I o r p r o d u c t s o f lower n u c l e a r i t y e.q. [Pd4(C0)5(PBun3)3-

(PPh3)l , depending upon r e a c t i o n c o n d i t i o n s . 210

w i t h [ P t ( C 0 ) 2 ] n i n aqueous a c e t o n e t o a f f o r d t h e t r i- and penta-

n u c l e a r p r o d u c t s [ P t 3 (CO) L 1 and [ P t 5 (CO) 6L41, [ L = PPh3, P ( a n i s y l ) 3 , P ( t o l ) 3, o r PEtPh21 .211 Some o r a l l of t h e ca rbony l

l i g a n d s i n p l a t inum ca rbony l phosphine c l u s t e r s can b e r e p l a c e d by u-S02 l i g a n d s , some r e a c t i o n s p roceed ing w i t h a change i n nuc lea r -

i t y . T y p i c a l p r o d u c t s are [ P t 3 (p-S02) (PR3) 31 (PR = PMe2Ph,

PCy3, PBun3) and [ P t 5 (CO) (p-CO) (p-S02) (PPh3) 4 1 . 212

r e a c t s w i t h MeSH, PhSH and H 2 S t o g i v e t h e nove l p r o d u c t s

[Pt3H (p3-SMe) (p-dppm) 1 [Pt3H (v3-S) (p-dppm) 3] ’, r e s p e c t i v e l y . 2 1 3

2 The f i r s t P-bonded

3 6 2

- 3 5

Phosphines r e a c t

3 4

The coordinatively-unsaturated c l u s t e r c a t i o n [Pt3(p3-CO) ( ~ - d p p m ) ~ l 2+

2+ , [ P t 3 (SPh) (p3-SPh) (p-dppm) 31 2+ and

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11 Complexes Containing Metal-Carbon 0- Bonds of the Groups Scandium to Manganese, including Carbenes and Carbynes

BY M. J. WINTER 1. Introduction

In this chapter, Cp’ represents CgH4Me and Cp* indicates C5Me5. Several reviews with material of general relevance appeared,

including articles on alkene polymerisationl, selected coordination chemistry of alkanes4 , and dimetallaalkane~~.

T complexes2, transition metals in organic synthesis3, the

2. Group 3 (Sc, Y, and La), Lanthanides, and Actinides.

Relevant material on thorium is contained in articles on C-H activation6 and lanthanides in organic synthesis7. for H-H and C-H bond activations at do metal centres, in particular

LuRCp2 , are considered in a theoretical analysis.

form derivatives of [ URCp3 I-. UCp3 to form U(COMe)C1Cp3.10 (R = Bun or Cy) undergo a elimination process to the corresponding hydride during mass spectrometry. l1

Two mechanisms

Organolithiums RLi (R = Bun, Me, Ph) react with U(Bun)Cp3 to Acetyl chloride oxidatively adds to

The rl 2-iminoacyls U[n2-C(Me)=NR]Cp3

Treatment of ScRCp*2 (R = HI Me, tol-p) with R’CN gives azomethine derivatives Sc{NC(R)R’}Cp*2. for R = Me with various R’CN resulting in Sc(NHR’)Cp*2, methane and R’NH2.I2 and M’R ( M ’ = Na, Li; R = CCPh, BuE) lead to M(R)Cp2.phenn. 13

Addition of RLi to MC1(THF){rl,rl’-C5H4(CH2)3C5H4} (M = La, Pr; R =

aryl and M = Nd, Y, La; R = But, CH2But) results in halide for aryl or alkyl rep1a~ement.l~ YbMe(THF)Cp with related But, CH2SiMe3, and tolyl complexes of Yb and Lu suggests trends in reactivity that were examined by hydrogenolysis . l5 YbclC~*~, YbClCp*, Bz2, and BzH Addition of the Grignard reagent BrMgCH2CHCH=CH2 to UClMeCp”2 gives the folded metallacyclopentene ~ i r 1 4 - c ~ ~ ~ ) ~ p * ~ while similar products are produced in the reaction of MC12Cp*2 (M = Th, U) with

Further reactions occur

Reactions of MC1Cp2.phenn (M = Nd, n = 1; M = La, fi = 2)

A comparison of the structure of

Addition of BzCl to Yb (OEt2 )Cp*2 results in the metastable YbB~Cp”2.l~


Complexes Containing Metal-Carbon a- Bonds (Sc 10 Mn) (THF)McJ(CH~CR=CRCH~) (R = HI Me). 17

Na, K ) with MeLi or Me3SiCH2Li gives bridging methyl derivatives of the type M(~-Me12Cp*~LiL2 (M = Lu, La, Pr; L = THF or TMED) or [Li(DME)3][M(CH2SiMe3)2Cp*2] ( M = Pr, Lu).'~ LiCH(SiMe3 12 to YClCp*2 (THF) results in Y {CH( SiMe3 12 )Cp*2. l9 Thermolysis of dialkyls Th(CH2SiMe3 )CP*~ or Th(CH2But)Cp*2 evolves SiMe4 or CMe4 and cyclometallated products T)h(CH2SiMe2tH2)Cp*2 or T ~ ( C H ~ C M ~ ~ ~ H ~ ) C P * ~ . ~ ~ equilibrium with Th (dH2SiMe2tH2 Cp*2 and SiMe4. 21

PhCCPh to S~(THF)~CP*~. insertion and C-H activation steps while forming (2).22 Thermolysis of [YHCp*2]2 in benzene or octane results in evolution of H2 and formation of a o,q5-CgMe4CH2 complex.23 MRzCp*2 (M = Th, U ) undergo facile double carbonylation with C=C bond formation to give monomeric or dimeric cis-enediolato complexes. Carbonylation of the 17 2-acyl ThCl ( T ~ ~ - C O C H ~ B U ~ Cp*2 gives enedionediolate complexes. 25

23 1

Treatment of a number of species M(~-C1)2Cp*~M'(ether)2 (M' =

Addition of

The e-alkyl Th(CH2SiMe3)2Cp*2 is in

The dimetallaalkene (1) is apparently formed on addition of

This reacts with CO by successive

The dialkyls

The 20-electron M(n2-C0R)2cpz is a precursor.24

Cerium metal reacts with RX (R = alkyl, allyl, aryl) in the presence of traces of I2 to form "RCeX" which reacts in situ with cyclohexanone to give Grignard type addition products, reduction products , and reductive coupling products. 26 Ce(acacl4 with four equivalents of RLi (R = Me, norbornadienyl, or Me2N[CH2]3) gives CeR3.3Li(acac) or Li3[CeR3(acac)3] but excess MeLi gives Li3Ce3~e6. 3Li (a~ac)~?. R1R2C=0 to UMe {N( SiMe3 ) 2} 3 results in U ( OCR1R2Me) IN( SiMe3 ) 2 13. 28

Treatment of

Addition of ketones or aldehydes

3. Group 4 (Ti, Zr, and Hf)

Structural distortions of hexacoordinate alkyl (Me and Et) titanium complexes are amenable to analysis by extended Huckel calculations. 29 transformations of alkenes catalysed by titanium and other metals.30 Some relevant material is in a review of the literature year 1983 on titanium3I while crystallographic data for organometallic titanium complexes are analysed and classified. 32 Derivatives of N-sulphonylated norephedrines are good ligands for chirally modified titanium methyl complexes. These species react enantioselectively with aromatic aldehydes.33

Alkyl complexes are key intermediates in


co -

( 3 )

\ R' Al'

a &;*- X

Y - O

/ 'R'

R ( 5 )

(4)

R

X

\ / 'RI

Zr- 0

Cp'Ti-Si nn ,,Ti Cp,

Complexes Containing Metal-Carbon o-Bonds (Sc lo Mn) 233

The stepwise bond dissociation enthalpies Dl(Ti-Me) and D2(Ti-Me) in TiMe2Cp2 established from thermochemical data and extended Huckel calculations are compared to the respective halides and h y d r i d e ~ . ~ ~ The isolated C-H stretches of M(CH2D)2Cp2 (M = Ti, Zr, Hf) are lower than any other studied methyl complexes and the C-H bonds in the hafnium species are the longest and weakest yet characterised by this method.35

The cation [ZrMe(THF)Cp2][BPh4] is produced by treating ZrMe~Cp2 with AgBPhq and is an active catalyst for the linear polymerisation of ethene. 36 dehydrogenative coupling of primary and secondary organosilanes and reacts with PhSiH3 to form Cpz(PhMeHS1 )Zr(~-H)2Zr(SiH2Ph)Cp2. 37 Double insertion of NO into one of the Zr-R bonds of ZrR2cp2 (R =

Me or Bz) gives the Zwitterion Zr(R)[ON(R)=NO]Cp2.38 heterobimetal species ( 3 ) undergoes alkyl for halide exchange to form ( 4 ) on treatment with MeMgBr.39

Cp, indenyl) with HBF4/0Et2 gives the 14-electron species TiMeL2 which form stable complexes with a number of nitrogen ligands or PMe3. Some of these react with CO or ButNC to give TiMe insertion products. 40 Cyclohexenyl lithium reacts with Zr(C1 IMeCp2 and PMe3 to form Zr(PMe3)[ n2-cc(cH,)4].41

Treatment of the e-alkynide Zr (CCPh)Cp’2 with Zr ( q4-C4H6 )CP’~ gives a compound with a delocalised metallacyclic system with, to a first approximation, two a,~-alkynyl units.42 The single electron reduction of Ti(CCPhICp2 is reversible and gives an anion which although stable at -3OoC, loses Cp- at 25°~.43

reaction of Zr(CHzPPh2 ) 2cp2 and RhH ( PPh3 ) 4. 4 4

zirconium species with Rh2 (CO) ( sBut 12 gives a hydroformylation active complex with CH2PPh2 bridges. 4 5 Thermolysis of zr[CHPh(sPh)12cp2 in toluene gives Zr(SPh)2Cp2 and trans-PHC=CHPh apparently by a clean first order process.46 ZrPh2(C5H4But)2 reacts with Se in a catalytic cycle which produces derivatives of benzene-1 ,2-diselenol. 4 7

Interaction of R ’ ~ A ~ X (R’ = Me, Et) with [ Z ~ ( ~ ~ - O C C H R ) C P ~ I ~ (R =

CH2But) gives an equilibrium mixture of ( 5 ) and ( 6 ) with bridging methyl ligands that reacts with HCCH or CO to form respectively alkenyl or acyl derivatives.48 Carbonylation of Ti(CH2CR’=CR)Cp2 (R, R ’ = various alkyls, SiMe3, Ph) in the presence of PMe3 gives n2-ketone species

Sterically hindered alkyl lithiums LiR(tmen) displace chloride

The =-methyl species ZrMe2Cp2 catalyses the

The

Acidification of TiMeL2 (L =

An “early-late” transition metal complex is formed in the Reaction of the same

The u - a r y l

an intermediate acyl Ti (CR=CRCH2C=O)Cp2. 49


from ZrC12Cp2 to form complexes ZrCl(R)Cpz which are the subjects of electrochemical studies. 50 In related reactions, LiCPh2OMe or MgClCH20Me and ZrC12Cp2 give the metallaoxiranes Zr(Cl)(CR2OMe)Cp2 (R = Ph or Me). Thermolysis of the phenyl derivative provides ZrCl (OMe)Cp2 and Ph2C=CPh251i while addition of [Zr the methyl complex affords ZrCl(OMe)Cp2 and ZrMe(C1 Addition of one or two equivalents of LiCH(SR')R to provides ZrCl[CHR(SR')lCp, (R = SiMe3, Ph; R' = Me, Zr[CHR(SR')12 (R = HI Ph; R' = Ph) respectively.53 Grignard reagents R"MgX (R" = Me, Ph, Bz) gives ZrR [CHR(SR')]Cp2.

The acetylide Zr(CCMe)ClCp'2 undergoes hydrozirconation with ZrH(CllCp2 to form Cp2Zr[C(Me)=C(H)ZrClCp'2] which has an agostic metal-a1 kenyl @-interaction. 54 Trimethylphosphine reacts with MC12Cp2 (M = Ti, Zr, or Hf) in the presence of Mg to form [M( PMe3 ) ( u- { q1 : 775-C5~4 } )cp] 2. 55

ZrH(C1 )Cp2 to form nl-butadiene complexes. incorporated at the B-position.56 by AgPF6 (X = C1) or T1PF6 (X = I) in MeCN provides the cation [Zr(Me)(NCMe)Cp2][PF6]. ZrF(MeICp2 occurs by fluoride abstraction from [PFgI-. Carbonylation of the cation gives [Zr(COMe) (NCMe)Cp2]+.57

form alkanes more quickly than the corresponding Cp*2 complex although when X = HI the reaction is very fast €or both.58 Complexes Cp2Zr( q,u2-RMeCO) (P-C1 IAlMe2 arise in the reaction of AlMe3 with ZrCl(COR)Cp2 (R = Me, Et).59

This requires a one hydrogen transfer to a former carbonyl carbon atom. 6o Cp2Zr(CH2CH2C5H4)Ru(C0)2 gives a ruthenium carbene complex. In a related reaction C P ~ ( O C ) Z ~ R U ( C O ) ~ ( C ~ H ~ ) ~ the Zr-C bond is cleaved by H2 to form Cp2HZrRu(C0)2Cp which rearranges further.61 Dipicolinic acid reacts with TiMe2Cp2 or T~Me2(CgHqCH2CH2~5Hq) to titanocene dipicolinate derivatives. 62 PhCCC02H under H2 gives T)i [ CPh=CH-C ( = O ) -A] Cp2. PhCCC02H. 63

Ethene, MeMgC1, and TiCl(indeny1) interact to form

Various enynes react with With ZrD(C1 )Cp2, D is

Halide abstraction of ZrMe(X)Cp2

In THF or CH2C12 rearrangement to

Dihydrogen reacts with ZrX(CH2But) ( n5 , q5 '-CgMeqCH2CH2CgMeq) to

Ketone

Treatment of Zr ( n2-OCtol 2 ) ] with PPh3=CH2 yields Zr (CH=PPh3 1 ( OCHtol2 Cp2.

Carbonylation of the heterobimetallic

Photolysis of TiMe2Cp2 and

Complexes Containing Metal-Carbon 0- Bonds (Sc to Mn) 23 5

Ti, Zr, or Hf) leads to C p 2 T w C H 2 . 6 5 r 6 6 addition of SiC14 gives (7 1. 67 two equivalents of PMe3 results in Ti (=CH2) (PMe3 )Cp2. 68

CH=CHCMe2 gives the metallacycle ( 8 ) . Complex ( 8 ) reacts with PMeR2 to form the carbenes Ti[=C(H)CMe2CH=CH2](PMeR2) and with AlMe2Cl to give ( 9 ) .69 results in (10). Other titanacycles give related products. The products of their thermolyses are consistent with intermediate a-substituted titanocene carbenes. 70 Addition of MeLi to

Cp2TkCH~Rh(cod )c'l results in (11). 71 The nature of hydrocarbons formed on thermal decomposition of

substituted titanacyclopentane derivatives and the byproducts of catalytic dimerisation of ethene by Ti(OBU)4-AlEt3 suggests successive formation of metallacycle and homoalkyls in the catalytic The synthesis of (*)-A(9,12)-caprielline using titanium derivatives involves the ring opening of a titanacyclobutane ring to an alkylidene/alkene derivative. 73 reaction of Mg(butadiene1 and ZrC12cp8'2 (Cp" = C5H4But) gives an equilibrium mixture of zi (CH2CH=CH6H2 )cp"2 and Zr ( 174-~4~6 )cp"2 which is reactive towards s8 and S ~ B . ~ * ZrC12Cp2 and BunLi gives Z~(BU")~CP~ which i s a source of ItZrCp2". Thus, its reaction with butadiene gives Zk(CH2CH=CHCH2)Cp2 and

Alternatively, Treatment of Cp2$iCH2TiCp2dH2 with

Treatment of Ti=CH2cp2 precursors such as Cp2TriCH2AlMe2dl with

Addition of norbornene to Cp2T-Cl

The

Salt elimination between

i

Zr ( T14-C4H6 )cp2. 75

Addition of Mg/Hg or Mg/HgC12 to HfC12Cp2 in the presence of alkynes RCCR ( R = Me, Et, or Ph) gives the metallacyclopentadienes Hlf (CR=CR-CR=kR)Cp2 which on HC1 treatment give E,E-butadienes. 76

Addition of ButOOH to Hf (H)RCpX2 gives H2 and Hf (OOBut) (R)Cp*2 while the metallacyles H'f([CH,]3CH2)Cp*2 and Hi(CH2CH(Me)bH2)Cp*2 undergo Hf-CH2 bond cleavage resulting in Hf (Bun) (OOBut)Cp*2 and Hf (CH2CHMe2) (OOBut )Cp*2 respectively. 77 H'f (CH2CH2tH2 )Cp2 gives an q2-ketone complex that has n-bonding character. 78 o-csH4 (CH2MgC1) (MgBr) gives the titanacycle Ti ( C G H ~ C H ~ - ~ ) C ~ ~ . '' Thermolysis of M(C6H4RI2Cp2 ( R = H, Me) gives benzyne intermediates that react with PPh3=CH2 to form two isomers each of

to give Zr ( PMe3 ) (

R ~ ~ ( C O ) ~ , Cr(C0I5, MO(CO)~, or W(CO)5] gives complexes with the general formula (12). Their decomposition products are ethene,

Carbonylation of

The reaction of TiC12Cp2 with the u-Grignard - Ti(C6H4R) (CH=PPh3)Cp2 and T ~ ( C ~ H ~ R C H ~ ) C P ~ , ~ ' Or with PMe3 (R = H)

cp2. 80 The reactions of Ti(q2-C2H4)Cp*2 with LnM(CO) [LnM = Mn2(CO)g,

Organometallic ,Chemistry 236

(10)

n Cp,Ti - - - Rh(codl

\/ CH3

(11 1

\ /"' CI

Complexes Containing Metal-Carbon a-Bonds (Sc to Mn) 237

LnM( CO) and unidentified titanium complexes. 81 Hydrolysis of TiMe3cp* gives successively [TiMe2Cp*]2( - 0 ) and

“l‘iMeCp*(p-O)l3, the latter of which has a Ti303 ring.82 lithium reagents (R = Me, CH2SiMe3, and C6F5) react with TiC13Cp* to form trialkyls TiR3Cp* and with MgClBz to form the corresponding tribenzyl. 83 In related reactions, ZrCl (CgMe4R) ( Q8-cot) (R = Me or Et) and R’Li (R = Me, Et, Bz) undergo R’ for C1 exchange.84

Treatment of MC14 (M = Ti, Zr, or Hf) with RMgCl (R = C1OHTMe-1) gives MR4.85 Grignard reagents or MgR2(THF)2 and MCl4 (M = Ti, Zr) undergo reaction to form MR4 together with a number of magnesium

[ ZrR4] 2- species that are probably polymeric. 87 deuterium labelling experiments on the polymerisation of styrene by ZrBzq-AlEt3 are consistent with a monomer insertion into a single M-C bond rather than into a metallacycle.88 Ti (CHZOCOR)~ result in the reaction of ROCOCH2Li and Tic14 .89 Addition of (Et2N)3P=CH2 to TiC14 in Et20 provides the violet cyclic double ylide (13) .go The cot complex Zr(THF)C12(cot) reacts with MesMgBr to form Zr(MesI2(cot), which subsequently carbonylates

Alkyl

Reduction of ZrR4 (R = Bz or Me) with BunLi gives The results of

The titanium alkyls

to [ Zr ( p, n2-Mes2Co) ( n-CgH8 12. 91

Addition of dmpe to zr(cH~SiMe~)~ results in Zr(CH2SiMe3)4(dmpe) which contains agostic hydrogen interactions. 92 Carbonylation of MMe2(OArI2 (M = Zr, Hf; OAr = OC6H3But2) and addition of pyridine probably proceeds bonds of a pyridine 1 igand.

DMF, or DMSO at low potentials in two-electron steps with the formation of titanium.94 100% yields of TiC13Me, a nonbasic Grignard analogue that has high selectivity and is more reactive than TiMe( OCHMe2) 3. 95 diffraction studies on TiCl3Me show the methyl group is symmetrically flattened (C3v) with H-C-Ti bond angles of 101.0 + 2.2O. This is perhaps a consequence of .rr-donor properties of C-H methyl bonds into low-lying M d-~rbitals.~~ Addition of dmpe to TiC13R (R = Me or Et) gives TiClR(dmpe). For R = Me the Ti-CH2-H bond angle is only 93.5O whereas the ethyl derivative has a Ti-C-C bond angle of 86.3O and an apparent Ti-CH2-CH-H system.”

insertion of an n2-acyl into the ortho C-H

The complexes TiPhZ and TiBz2 both reduce irreversibly in MeCN,

Addition of MeLi or MeMgCl to Tic14 gives

Electron

- There is relevant material in reviews on crystallographic data

238 Organometallic Chemistry tor niobiumg8 and tantalum.99

Addition of MeLi to TaC12Cp*2 results in Ta(H)(=CH2)Cp*2 in which all three hydrogens of the hydride and methylidene group undergo exchange. loo TaMe(CO)Cp*2 y& the 16 electron species TaMeCp"2. with CH2PMe3 to form Ta(CH2PMe3)(Me)Cp*2 which loses PMej to form TaMe(=cH2)~p*~. Addition of (HzC=CH)MgBr to TaC12Cp*2 gives Ta(H) (=C=CH2)Cp*2 which carbonylates to form Ta(CH=CH2) (CO)Cp*2 y& Ta(CH=CH2)~p*2.100 oxidative coupling process to form ib[C(Me)C(Me)C(Me)kHMe]Cp2 whose structure may be written with several resonance forms.lol

T a M e 3 ( ~ i M e ~ ) C p * . ~ ~ ~ The n2-acyl TaC13 (r12-C0SiMe3)Cp* reacts with pyridine at the acyl carbon to give TaC13 [ q2-OCSiMe3 (py) ]Cp* ; the pyridine group exchanges with pyridine-d5. Io3

Carbonylation of Ta (HI (=CH2 ) Cp*2 gives It also reacts

Excess MeCCMe reacts with NbH3Cp2 by an

Treatment of TaC13(SiMe3)Cp* with MeMgBr gives

Addition of ethene to v(cloH8)Cp gives the metallacycle V[(CH2)3CH2]Cp which subsequently dimerises to (14) which has fourfold alkyl bridging. An analogous methyl species [VMe2cp*I2 is formed by treatment of VMeCpCp* with MeLi. I o 4

1

Methyl lithium reacts with TaC13 ( OAr) (OAr = 0CgH~Bu~3-2 4,6 to form TaMe3(0~r)~. Thermolysis of this compound results in methane evolution and the formation of (15) while photolysis gives TaMe(=CH2) (oArI2 and methane. undergoes intramolecular addition of a But C-H bond to the Ta=CH2 group.lo5 insertion process to form TaEt (H) ( OSiBut3 ) 3. ethene reacts with Ta ( =CHBut 1 (THF 1 ( OAr 13 ( OAr = 0C~H3Pr~2-2 6 1 to form the metallacycle Ta(CH2CH2CHBut 1 (OAr )3 and with styrene to form Tk ( CHPhCHButbH2 ) ( OAr ) 3.

Treatment of this species with CO gives the oxide T ~ ( = O ) ( O S ~ B U ~ ~ ) ~ and the dicarbide (But3SiO) 3TaCCTa( OSiBut3 13. Ta(=O) ( 0 S i B ~ ~ 3 ) ~ causes a C-H activation and formation of TL(H) (CMe2SiBut2;)) (OSiBut3)3.108 Isonitriles CNAr' (Ar =

C6H3Me2-2 6 or CgH3Pri2-2, 6 R = Mer Bz) or TaB~2(0Ar)~ to form n2-iminoacyls

On standing the final complex

Excess ethene reacts with Ta(HI2(OSiBut3)3 by an On the other hand

Sodium amalgam reduction of TaC12(0SiBut)3 gives Ta(OSiBut3)3.

Thermolysis of

react with Ta ( OAr 2R3 ( OAr = OC6H3Me2 ;

Ta ( n2-Ar 'NCR 2R ( OAr 2 or Ta ( q2-Ar 'NCR 12 ( OAr 1 3. 109

5. Group 6 (Cr, Mo, and W)

A review on cluster chemistry contains relevant material.110


Electroreduction of Cr(C016 gives the 19-electron radical anion

The reaction of aqueous Cr(I1) ion with [Cr(C0)6]-. which is trapped by Bu3SnH to give the formyl [Cr(CHO) (CO)5]-.111 ICH2CONH2 leads to [ Cr (CH2CONH2 ) ( OH2 ) ] 2+ which on acid treatment gives [Cr(CH2CO2H) (OH2)5]2+ and eventually [~r(0~2)~12+.112 Addition of Hg2+ to [Cr(CH2CN)(OH2)5]2+ in water results in [Cr ( OH2 ) ] 2+ and HgCH2CN+. [Cr(CO),]- (n = 3 - 5 ) and a number of haloalkane derivatives proceeds by insertion into the C-X bond followed by a 6-H-shift.114

[MoC1( n3-C3H5 ) 12 as Mo(CHMeCH2H) (q3-C3H5 12 is formed, this product has an agostic hydrogen interaction. 115 [IMS(THF)nC1}2{2-CH2C~H4)2}] reacts with WCl4O to form paramagnetic M9(THF)4(ow(2-cH2c6H*}2)2. 116 followed by water and oxygen to MoBr2(0)2(bipy) results in R for Br exchange to give MoR2 (0) (bipy ) . M(Me)(N2Et)(R,PCH2CH2PR2) (M = Mo or W, R = aryl) in the reaction of M(Br)(N2Et)(R2PCH2CH2PR2) with Me1 proceeds by an Sn2 process with the tungsten system reacting faster than the molybdenum. 118 Addition of FcLi to WC140 results in replacement of at least three chlorides as all the permutations of WX(O)(Fc)3 (X = C1, OFc, or OBun) are formed according to the reaction condition^.^'^ of AlMe3 to Mo2C1202 or MoC13O(THFl2 gives species apparently containing Mo(u-CH2)Al groups that are useful €or in situ "carbonyl olefinations" to form RC(=CH2)R from ketones RC(=O)R. 120

Ethene inserts into the formaldehyde-tungsten bond of W(H)~(Q~-CH~O) (PMe3)4 s o forming the unstable metallacycle ~ ( C H Z C H ~ C H ~ ~ ) (C2H4 l 2 (PMe3)2.121 WH(q2-CH2PMe2) (PMe3)3 is also a very reactive species.122 The W-H bond of WH(CO)2[P(OPr1)3]2(NO) undergoes insertion with alkynes HCCC(=O)R ( R = H, OMe) to form W(CH=CHCOR) (Co)2[P(OPri)3]2(NO) .123 Alkyl methacrylates CH2=C(Me)(C02R) react with MoHq(dppe12 under thermal or photolytic conditions to give a fluxional, probably seven coordinate, structure M&H[CH=CMe-C(OR)=6] (dppeI2. 124

catalysts for the metathesis of carbodiimides, apparently i[C(=NR1 )CR2i(=NR31 (CO)5 intermediates

The gas phase reactions of

Magnesium chloride is eliminated during reaction of PrlMgCl with - The di-Grignard

Addition of RMgBr ( R = alkyl)

The formation of

Addition

The related

Some W(I1) imido, carbene, or isonitrile complexes are active

A review on the 02r4 triple bond for Mo and W contains relevant Addition of alcohols (R'OH) to M2R2(NMe2)4 (M = Mo or

W, R and R' = alkyl, R with no B-hydrogens) results in OR' replacement of the NMe2 groups. When the R and R' groups are


(18) (19)

\ Me Me H

( 2 0 ) (21)

&Me &Me

OMe \

(0Cl4Cr= C OMe

\ (OC),Cr = C (OC &Cr = C

OMe \

Complexes Containing Metal-Carbon a-Bonds (Sc to Mn)

smaller, the reaction proceeds to M2(OR*)6.127r128 Diaryltriazenes ArNNNHAr (Ar = Ph, tol) react with w ~ E t ~ ( N M e 2 ) ~ to give three isomeric f Orms of W2Et2 (NMe2 ) 2 (ArN3Ar ) 2. 29 MgBz2 to either MoCl4 (THF ) 2 or Mo2 ( OPri 6 gives the Mo,=Mo bonded M02Bz6 which has an unbridged ethane like geometry.13’

24 1

Addition of

ThermolYsis of W2C13(NMe2)3L2(lJ-HCCH) ( L = PMe2Ph or PMe3) gives the bridging vinyl complex W2(NMe2)2C13(lJ-CH2NMe)(U-CH=CH2)L2. The vinyl arises through hydrogen transfer from a coordinated NMe2 group to the bridging HCCH function.l3l number of alkyls) to trans-(Mo6Clg)C14(PR3)2 ( R = alkyl) results in formation of ( ~ 0 6 ~ 1 ( ~ 1 ~ - ~ (R pX 1 ( P R ~ 1 2 (

hexacarbonyl reacts with U[=C(HyPPhMeRlCp3 to form the vinyl (16) which undergoes a rearrangement on thermolysis to form ( 17 1.133

Addition of AlR’3 (R = a

= 2 or 3 1.132 Tungsten -

A knowledge of the heats of reaction between M0Me(C0)~cp with Me1 and related reactions allows estimation of the Mo-Me bond strength as 47 kcal m01-1.134 on EtI gives CrEt(C0)3Cp. SO2 to form Cr(S02Et)(C0)3Cp and substitution with P(ORI3 (R = Me or Et) to give CrEt(CO)z[P(OMe)3].135 [~yclenPH~][W(Co)~Cp] (cyclenPH = cyclenphosphorane) reacts with Me1 to form WMe(C0)3Cp and [cyclenPH2] [I].136 [ ( OC ) 3Mo ( C5H4Si {Me } 2 C5H4 ) Mo ( CO 1 3 ] 2- undergoes a 1 ky la tion at both metal atoms to form the anticipated dialkyl species.13’ fulvalene complex [ ( O C ) ~ M O ( C ~ H ~ - C ~ H ~ )M~(co)~ 12- undergoes similar reactions with RX (RX = MeI, BzBr, or ClCH20Me) while with I(CH2I3I the product is the carbene (18). Thermolysis of (18) gives propene.138 Reduction of t ( O C ) ~ M O ( C ~ H ~ - C ~ H ~ )~o(co)~(PMe~)~]+ gives the methyl [ (OC)3Mo(C5H4-C5H4)MoMe(CO) (PMe3)2] Treatment of MoMe(CO)3(C5H4[C=kHC(OH)CH26H2] with acid followed by W(C0)3(NCMe)3 leads to a heterobimetal lic fulvalene complex. 139

Picosecond flash photolysis of WR(C0)3cp ( R = Me, Et) leads to

WR(CO)2Cp within 25ps of photolysis whereas microsecond flash photolysis of WEt(C0)3Cp forms W(CH2CH2H)(C0)2Cp with a kl of about 1.5 x lo5 s-l. Similar photolysis of WMe(C0)3Cp in THF gives me(C0)2(THF)Cp which possibly undergoes a-elimination to form W(H) (=CH2)(C0)2Cp.140 Photolysis ( A > 380 nm) of WMe(C013Cp in an inert solvent in the presence of PPh3 gives [PMePh31[W(C0)3Cp] and WMe(C0)2(PPh3)Cp.141 Photolysis of MoMe(C0)3Cp in the presence of CpH at 213K gives MoR(CO)( 4-CpH)Cp (R = Me and COMe), MoH(COMe)Cp2, and other products.142 The acyl product is reactive with a number of dienes so forming n3-allyl ~omp1exes.l~~

Nucleophilic attack of [Cr(C0)3Cp]- This species undergoes insertion with

The complex

The dianion

The


Substituted arenes M(ql-Arf )Ln (Arf = CgF5, CgNFq) arise in reactions of Arf F with [ w (co ) 3Cp]-. 144 react with Mo(CH2CH2C5H4) (Co)3 to form r12 and r14-diene complexes.145 nitrosonium insertion into the Cr-Me bond to form [ Cr t N ( =CH2 ) OH} (NO) 2Cp]+. 46

(I?’ = Me, OMe, Phi R‘3 = PhMe2) results in formation of Mo(OS02CF3) (C0)2(PR’3)Cp.147 results in [MO(C0)2(MeCHO)Cp]- y& formyl and hydrido acyl intermediates. the Presence of PPh3 gives [Mo(CHMePPh3) (C0)2(PPh3)Cp][BF4] whereas addition of Me1 in the presence of L ( L = CO or PPh3) gives MOM~(CO)~LCP.~~* As more Me groups are incorporated into the ortho positions of substituted MoBz(C0)jCp molecules, the Mo-CH2-C(ipso) bond angle increases. This is correlated to the greater reactivity towards carbonyl insertion observed with more methyl groups.149 Heats of reaction for insertion reactions of MoR(C0)3cp (R = Me, Et) with PR3 show insertion is favoured for more basic PR3 and for Et over Me. 50 The reaction of MoMe (CO) 3Cp with Fe (CO 12 ( PPh2 1 Cp gives Cp(OC)2Mo(u-PPh2)(p-X)Fe(CO)Cp (X = H and COMe).151

[PPh3][I]) are available through interaction of [M(CO)3Cp*]- and reagents such as ICH2C1, C1CH20Me, and CH2Br2.152 Addition of Zr(R’)(Cl)Cp2 (R’ = H, Ph) to W(CHRCOX)(C0)3Cp (X = OEt, H, Me or Ph) gives alkyl ( 1 9 ) which loses R’CH=CHR to form Cp(OC)3W-O-Zr(C1 )Cp2.153 gives high yields of Cr(CH2Cl)(N0)2Cp. Addition of AgBF4 abstracts C1- and results in insertion of the CH2 group into a Cp C-H bond so forming [ Cr (NO 1 2Cp ‘1’.

HBF4 gives the cation [W( o2-H2C=CMe2) (cO)3Cp]+ W(CH=CMe2)(~o)3~p. W(CH2CHMe2) ( ~ 0 ) ~ C p . l ~ ~ [Mo( n2-PhCCPh) {P(OMe)3}Cp]+ gives the vinyl Mo (CH=CH2 ) ( v2-PhCCPh) {P ( OMe ) 3 } which undergoes thermal ly promoted a-elimination reactions which generate q3-cyclopropenyl and n4-cyclopentadiene complexes. 156 = Cp or Cp*) shows extensive reactivity towards NO, ClNO, and CF3CO2H; thus acidification by CF3C02H of either complex gives ~(CHZCH~COM~) (02CF3)2(CO)L.157

Butadiene or other dienes

Addition of NOW6 to CrMe(N0)2Cp results in

Addition Of ROS02CF3 (R = H, Me, or SiMe3) to MoMe(CO)2(PR’3)Cp

Addition of LiEt3BH to MoMe(C0)3Cp

Addition of [M@30][BF4] to [MO(C~)~(M~CH~)C~]- in

The complexes M(CH2X)(C0)3Cp* (M = Mo or W; X = halide, OMe, and

Addition of CH2N2/Cu to CrCl (N0)2Cp

Treatment of [W(CO)3~p]- with methallyl chloride followed by the vinyl

Borohydride addition to the vinyl complex gives Addition of (CH2=CH)MgBr to

The vinyls h(CH=CHChMe) (C0)2L [L

Addition of CO2 to ( 2 0 ) results in


loss of PMe3 and formation of (21).158 Addition of RCCR (R = C02Me or CF3) to W(X')(CO)3Cp (X' = AsMe2;

R = C02Me, X' = SPrl; R = CF3, X' = SPr") gives metallacycles h[C(O)CR=CRk*] ( C O ) ~ C P . ~ ~ ~ Addition of tolLi to Mo(CO12 (N0)Cp provides the acyl [Mo(COtol) (CO) (NO)Cpl- which reacts with [Fe(CO)2(THF)Cp]+ to give a bridging acyl complex. 160 (MeI, [Me30]+, MeCOBr) or arylation (PhCOBr) of [Mo(C0)3Tp']- gives MO(T~~-COR)(CO)~T~' [R= Me or Ph; Tp' = HB(3,5-Me2-pz)]. labelling studies show that a metal carbonyl is lost in this process. isomeric tricarbonyl .161 Photolysis of Mo(COCH2R) (C012Tp (R = H, Me) in the presence of P(OPh)3 gives M(COCH2R)(CO) (P(OPh)3}Tp while treatment with BunLi and BzBr gives Mo (COCHBzMe 1 (CO) 2Tp.162 Ring opening of, and PMe3 loss from w(n2-CRC0)(CO)(PMe3)Cp (R = tol-p) occurs on reaction with Et2NCCMe which gives a ketenyl complex W [ n1 -C (R =C=O) (CO ( n2-Et2NCCMe 1 Cp. l6

Electrochemical reduction of [Mo ( NCMe ( n2-MeCCMe 1 ( indenyl ) 1' results in p-(o,n3:n3,o-~g~e~) complexes.164 reduction of [Mo(RCCR)~L]+ (L = Cp, indenyl) and reactions with - O - C ~ H ~ ( CH=CH2 ( PPhZ ) result in C-c bond formations. 16 5 An X-ray diffraction study on CP*(Me3)W(~-NN)W(CO)~Cp shows the W-Me bond trans to the N2 ligand is longer than those cis.166 of [Mo (CO 1 { NR*=C( py ) H} ]Cp' gives optically active complexes. 167

Alkylation

Isotopic

The n2-acyl is apparently not in equilibrium with the

One electron

Acidification

Addition of MeOH to W(H)(Ph)Cp2 gives the methoxy species W(H)(OMe)Cp2. the presence of wet C02 to form the appropriate W(H)(OR)Cp2.168 Ammonium iodide reacts with WMe2cp2 to give W(I)(Me)Cp2, which in turn reacts with PhMgBr to form W(Me)(Ph)Cp2. Addition of Fc+ gives the radical cation [W(Me 1 (Ph)Cp2]+ which undergoes a 1,2 shift as a hydrogen radical is abstracted by Ph3C'/MeCN in forming W ( B Z ) ( N C M ~ ) C ~ ~ . ~ ~ ~ Mo(H12Cp2 gives the vinyl Mo(Cl)(CR=CHR)Cp2 (via the corresponding hydride), do[CR=CH-C(O)b]Cp2, and Mo( T ~ ~ - C H R C H R ) C ~ ~ . ~ ~ ~

Treatment of [M(CO)3(n-C7~7)]+ (M = Cr, Mo, W ) with OMe- proceeds by two processes. The first involves fast reversible attack at a carbonyl (or at M followed by rearrangement) to form M(Co2Me)(CO),(,-C7H7) while the second is a slow addition at the ring to give the ultimate product M[n6-C7H7(OMe)] (C0)3.l7l

methods for metal carbene transformation^^^^, formation of metal carbon multiple bonds from a l k y n e ~ l ~ ~ , metathesis catalysis174,

Other alcohols such as EtOH or PrOH only react in

Addition of RCCR (R = C02Me) and CHC13 to

There is relevant material on carbenes in reviews on catalytic


tungsten carbenes related to W(CHBut) ( O C H ~ B U ~ ) ~ B ~ ~ ’ ~ ~ ‘ and electrophilic metal carbenes in catalysis.176

Calculations on the electronic structure of the Cr(CH2)+ fragment suggests a single a-donor bond from the CH2 to the high spin d5 Cr metal with no backbonding.17’ The results of extended Huckel calculations on Cis carbene alkene complexes W(=CR2) (alkene) (COI4 help to determine optimum configurations.17’ Transient resonance Raman spectroscopy suggests the unsaturated fragment produced on photodissociation of W[=C(OMe)PhI(CO), rearranges rapidly to a species in which there is a partial bonding interaction between the methyl and the metal. 179

= various halide, OCH2But) species act as Wittig reagents in reactions with R3R4C=0 which result in R1R2C=CR3R4. 180 carbene complexes active as metathesis catalysts apparently arise in the reactions of WC14(0Ar)2 with SnR4 (R = Me, Bun) or PbBu”4 while reaction of MgNp2.dioxane with W(C1)4(OC6H3Ph2-2,6) in Et20 gives isolable ~ ~ 1 2 ( o c ~ H ~ P ~ ~ - ~ , ~ ) ( c H B ~ ~ ) (OEt2) -181 The reactions Of WC13(=O)(THF)2 or Wc14(=0) with MeL proceed by MeH elimination to give solutions probably containing W(Cl)(=CH2)(=0) or

W(C1)2(=CH2)(=0). cyclohexanone while the second also metathesises alkenes. 182 Addition of PhCCPh and lr8-C10H6(NMe2)2 to W(C1)2(=CHPh)(CO)(PMe3)2 gives W ( C1) 2 (=CHPh) ( r12-PhCCPh (PMe3 ) 2 y& the carbyne W(C1) (CO) (PMe3)2(CPh) (n2-PhCCPh) The reaction of Bu3P=CH2 with Mo(Mes)2(=0)~ results in Mo(Mes)[=C(PBu3)L](=O)2 y& the charac te ri sed Mo ( CH2 PBu ) ( Me s ) ( 0 ) 2.

W2(CO)lo(p-CHPh) together with Cis- and trans-PhHC=CHPh, W(CO16, and Me-Ar. The reaction rate increases with electron donating groups on the Ar group.185 Photolysis of w ( c o ) ~ / c H ~ c ~ ~ in the presence of Me3SiCCH followed by treatment with MeOH/Si02 affords W[=C(OMe)Mel(CO)5 while photolysis under similar conditions but in the presence of HCC(CHZ)~OH gives 6[=C(CH2)3b](C0)5 in low yield.186 Addition of PhLi followed by [Me30]+ to W(CNBut) (C0)5 results in &-W[C(OMe)Phl (CNBut) (CO)4.187 Thermolysis of W[=C(NR2)SiPh3](CO)5 [R2 = Me2, (CH2I5] gives stable 16-electron carbenes W[=C(NR2)SiPh3](CO)4. The sixth octahedral site is occupied by a Ph group in a weak interaction.188 W[=C(NMe2)tol-p](co), results in D incorporation into the

Various w(x)~(Y)~(=cRlR~) (R1, R2 = various H, alkyl, aryl; X, Y

Unisolable

These solutions methylenate acetophenone and

Thermolysis of W(=CHAr)(CO)5 (Ar = Ph, tol, ~ 6 ~ 4 0 M e ) gives

This is reversible on CO treatment.

Addition of LiNPri2 followed by D20 to


E-N-methyl group only. W[=C(NMeBz )tol-~] (C0)5.189 R1CCR2 gives substituted hydronaphthoquinones in reactions whose regioselectivities may be discussed in terms of electronic and steric effects.lgO Cr =C ( OEt CH2PPh2 ] (CO 15 gives Cr [ =C ( OEt 1 C ( OEt 1 (Bun) CH2PPh2 I (CO 14 and Cr[=C(OEt)C(OEt)=CHPPh2 ] ( C O ) ~ . ~ ~ ~ Cr[=C(OMe)CMe=CH2] (COI5 to give a 60:40 mixture of the isomeric pentacarbonyls (22) and (23) together with the tetracarbonyl (24).lg2 its ability to polymerise alkenes by an interaction which weakens the intramolecular metal alkene bond.lg3 carbene (25) gives three isomeric dienes [PhCH=COEtI2, the tricarbonyl Cr(C0) 3['1 6-C6H5CH=C(OEt)C(OEt)=CHPh] corresponding u - C r ( C O ) 3 species. lg4 Cr[=C(oMe)C6H4F2-2,6](CO)5 results in cycloaddition forming cyclobutenone Cr(C0I3 complexes. Cr[=C(OMe)C6H4Me2-2, 61 (C0l5 gives carbene annulated products.lg5

azaallenylidenes [M(=C=N=CR2) (CO),]' while reaction of Cr ( CNCCl3 (CO) 5 with AlCl3 affords [Cr ( =C=N=CC12 1 (CO 15 1'. lg6 Treatment of c ~ H ~ c ( O M ~ ~ ~ C H = C H B ~ C ( O M ~ ~ ~ with ButLi followed by M(CO)6 (M = Cr, W) give the carbenes ( 2 6 ) while simpler 1,4-benzoquinone derivatives provide ( 2 7 ) that undergo annulation with alkynes to form B/C rings of anthra~yc1inones.l~~ reaction of A12Br6 with &-M[=C(NR2)0Et](Co)4 (R = CY, Pri; M =

Mo, W) gives [CH(NR2)(0Et)][M(Br)3(CO)4.198 Addition of LiEt3BH to either MoI[=C(CH2)30](CO)2L (L = Cp or

Cp') or Mo{(CH2)3Br}(C0)3Cp gives (28; X = 0 ) and the ally1

Mot (CH2 )3Br } (CO) 2 (PPh3 )Cp gives only Mo(C0) (PPh3 1 ( q3-C4H7 )Cp. lg9 The reaction of [M(CNMe)(C0)2~p]- (M = Mo, W) with I[CH2I3I gives &-MI[=C(CH2)3NMe](CO)2Cp complexes that react with LiEt3BH to form (28; X = NMe) .200,201. The carbene anion [ M o { = C ( C H ~ ) ~ N M ~ } ( C O ) ~ C ~ ] - protonates to form the hydride MOH{=C(CH~)~NM~}(CO)~C~ which subsequently undergoes a 1,2 hydrogen shift to form (28; X = NMe).202

Addition of LiCCMe to [M(C0)2Cpl2 (M = Mo, W ) followed by MeOS02CF3 gives complex (29 1. 203

High oxidation state molybdenum and tungsten alkylidyne complexes are reviewed204 while an alternative mechanism for

Reaction with BzBr instead of D20 provides Reaction of Cr[=C(OMe)Phl (C0)5 with

Addition of BuLi followed by [Et30]+ to

Cyclopentadiene reacts with

Addition of A1Et3 to W[=C(OEt)CH2CH2CH=CH2] (CO)4 enhances

Thermolysis of the his

and the Addition of PhCCPh to

The corresponding reaction of

Addition of BF3 to M[=C(N=CAr2)OEt](CO)5 (M = Cr, W) gives the

The

MO(CO)~(~~- C H 7) L whereas the reaction with


O E t OMe

(OC),Cr \ VPh 'Ph M (CO),

Me0 OMe OEt

(25) ( 2 6 ) M = C r , W

( 28) X= 0 , NMe; R = H, Me

M e 0 OMe Cr(C0)5

Me Me

(29)

NHMe-, OR

OR NH Me,

(30) R = H , SiMe, (31)

0

Complexes Containing Metal-Carbon 4- Bonds (Sc to Mn)

polymerisation and metathesis of cyclopentene by WCl6 and RCCH involves WC13 (CR ) carbyne complexes. 205

Catalytic quantities of WCI3(DME)(CBut) cause the polymerisation of cyclopentene to poly-1-pentenylene which has predominantly ( 7 5 % ) trans C=C bonds but metathesises oct-1-ene to ethene and predominantly trans-7-tetradecene. 206 Addition of CyNCO to wcl3(DME) (CBut) gives dC13(NCy) [N(Cy)C{C(Butl=C=Oib] .207 The neutral complex W IOCMe ( CF3 ) } ( =CHBU~ 1 (=NR (DME 1 metathesises hex-3-ene and cis-pent-2-ene very effectively and reacts with R’HC=CHz (R’ = H, SiMe3) to form (30).208

But metallacyclobutadiene ring is deprotonated (R = Ph) by NMe3.209 Addition of MeCN to W(dipp)3(CBut) (dipp = OC6H3Pri2-2,6) results in a metathetical reaction providing [W(dipp) 3(N) I x and ButCCMe.210 Carbonylation of W (OBut 1 (CNMe2 ) affords [ W ( OBut 3 (11 -0CCNMe2 12 but in the related reaction of W (OPri) ( p y ) ( CNMe2 ) the product is (0Cl2( OPri)W(p-OPri )3W(OPri)2(q2-Me2NCCNMe2) through the coupling of two alkylidynes.211 = alkyl , CF3 ) gives M( OOCR) ( CBut chemistry with alkynes.212 Treatment of W 2 ( d m ~ ) ~ (dmp =

CgH3Me2-2,6) with three equivalents of RCCR ( R = Me, Et) results in the tungstenacyclobutadiene W(C3R3)(dmp)3. Treatment of the latter with HC1 gives WC13 (C3R3 1. 213 W2(OPr1)6(NHMe2)2 and pyridine affords (31) at -20°C but u3 carbyne clusters W3 ( p3-CEt) ( p2-OPri 13 ( OPri 6 and bridged cyclobutadienes ~2 ( U-C4Et4 1 ( q2-C2Et2 (Opri 1 6 at ambient temperature. 214

[ (OC)5W(CNMes2-]2 from [W(=C=N=CMes2) (CO)5]+ and Br- is the radical W(CNCMes2) (c0)5.215 There appear to be three different mechanistic pathways for substitution of a carbonyl ligand in trans-MX(C0)4(CR) (X = halide, SePh; M = Cr, W; R = Me, aryl, NEt2) by PPh3.216 Treatment of tranS-WX(C0)4(CNR2) (R = Br, R = Cy; X = C1, R = Cy, Pri) with sources of Br- or C1- gives mer-[W(X)2(CO)3(CNR2)]-. incoming halide is easily replaced by PPh3 to give neutral carbyne species.217 The reaction of WBr(C0)4(CNCy2) and [=bN(Ph)CH2CH2NPh]2 gives the anionic carbyne - mer-[WBr2(Co)3(CNCy21]-.218

Addition of AsPh2- to WBr(CO)2(CNEt2)(bipy) results in AsPh2 for Br exchange. 21 followed by NH4C1 affords a carbyne intermediate which subsequently

247

The compound W[ OCH (CF3 ) ] ( DME ) ( CBut reacts with RCCH (R = Ph I to form tungstenacyclobutadienes W ( CButCHCR 1 [ OCH ( CF3 ) 2 ] 3 whose

Treatment of M(CH2But)3(CBut) with RCOOH (R which displays extensive

Addition of EtCCEt to

An intermediate in the formation of WBr(C0)4(C-N=CMes2) and

The

I

Treatment of WC1 (CO 2 ( py 12 ( CPh with Na2S2CNEt2


rearranges to the phenylketenyl [W(PhCCO) ( C O ) ( S ~ C N E ~ ~ ) ~ ] - . On the

other hand reaction using [NH2Et2][S2CNEt2] instead of the sodium salt gives the thioaldehyde W(C0) (PhCHS) (SCNEt2)(S2CNEt2) by an unknown mechanism. 2 2 0

Treatment of MCl(C0)4(CPh) (M = Mo, W) with excess P(OMe13 leads This reacts with dppe in a stepwise fashion to MC1[P(OMe)3]4(CPh).

forming MC1 [P(OMe 13 ] 2 ( CPh)dppe f ol lowed by MC1( CPh 1 (dppe 12. 221

G(C0) (PHPh2) (CHRCOOPPh2)Cp.222 [SMe2(Mes)][BF4] to form the cation (32) which reacts with excess reagent to form [ W (CO) 2 {T-I 3-S (Me ) C( to1 ) SMe}Cp] '+. 223 of W(C0)2(Ctol)Cp whilst irradiating with ultraviolet light affords ( 3 3 ) while use of PPh3 gives ( 3 4 ) which carbonylates to the q l-ketenyl W[n '-C (to1 CO 1 (CO 1 ( PPh3 ) Cp. 224

alkyne complex [ W ~ ( ~ - ~ ) ( ~ o ) ~ ( ~ - t o l ~ c t o l ) ( c ~ ~ ~ ~ ~ ~ ~ - l , 2 ) ~ ] ~ whereas for R = Me, in the presence of PMe3, the product is the ketenyl W(C0) (PMe3) {=c( to1)-C(=O)} (C2BgHgR2 - 1 , ~ ) .225 tran~-[Pt(H)(acetone)(PEt3)~]+ (R = Me) gives the W=Pt species (q6-C2BgH8[CH2R]Me2) (OC)2WPt(PEt3)2 which is further reactive with PMe3 or Co.226

Addition of PHPh2 to W(C0)2(Ctol)Cp gives W(C0)2(CHRPPh2)Cp and The same carbyne reacts with

Carbonylation

Acidification of [W(CO)~(Ctol)(C2BgHgR2-l,2)]- (R = H) gives the

Reaction with

Reaction of K[R'B(Pz)3] (R' = C3H3N2, H) with WBr(C0)4(CR) leads to W(C0)2(CR){HB(pz)3}, which are precursors for clusters with u3-CR groups.227 F e ~ ( c 0 ) ~ gives F ~ ( C O ) ~ [ T - I ~ - W ( C O ) ~ ( C ~ O ~ ) {HB(pz)3}] in which the WCtol bond acts formally as a four electron donor to iron. This compound carbonylates to give the corresponding Fe (CO) 4 complex. 228 Treatment of Fe (CO) 3 [T-12-w(co 1 (Ctol 1 {HB (pz 1 1 I with PHPh2 results in PHPh2 for CO substitution at iron to give a complex which on thermolysis gives (35).229

W(C0)2(CSMe) {HB(~z)~} gives the q2-ketenyl W(C0) (PEt3) [q2-C(SMe)CO] {HB(pz)3} which reacts with MeS03F to provide [W(CO) (PEt3) (q2-MeSCCOMe) {HB(pz)3} addition of CF3COOH to W (CO 2 ( CSMe 1 { HB ( pz 1 3 } gives [ W ( C O ) ~ ( = C H - S M ~ ) { H B ( ~ Z ) ~ } ] + which reacts further at the carbene atom with SR- and other donor ligands, but with primary amines NHR2 to give stable carbynes W(C0)2(CNR2) {HB(pz)3}.230,231

u-allylidene complex Mo2(CO)4(p-C3H2Me2)Cp2 which thermally rearranges in toluene/hexane or wet MeCN. 232 reacts with allene or 1,l-dimethyl allene to form =-ally1

The reaction of W(C0)2(Ctol) {HB(pzI3} with

Addition of PEt3 to

On the other hand

Addition of 3,3-dimethylcyclopropane to [Mo(C0)2CpI2 gives a

The u-allylidene also


co l3

to\ I c

a -


complexes but follows other reaction pathways with pentadiene and a1 kynes . 33 Treatment of [ Mo ( CO 1 2Cp2 ]

anion [ M o ~ ( c ~ ) ~ ( ~ - ~ ~ - c c P ~ ] - . give species rearrange thermally to MO~(CO)~(LI-P~CCH)C~~ (R = H) or to

Mo2 (co) M o ~ ( C O ) ~ ( P P ~ ~ ) (v-HCCH)Cp2 undergoes a phenyl migration form phosphorus to a carbonyl ligand followed by a benzoyl to alkyne migration in producing (36). 235 between MoX (q 2-F3CCCF3 )Cp and butadiene is (37 1. 236

precursor for the synthesis of heteronuclear cluster complexes in which the &-CR ligand is often present.237 Addition of Fe2(C0I9

to Mo(C0)2(Ctol)Cp affords the p-alkylidyne C ~ ( O C ) ~ M O ( I . ~ - C ~ O ~ ) F ~ ( C O ) ~ which is reactive towards CH2N2, 02, or s8.238 p-alkylidyne C P ( O C ) ~ W ( ~ - C M ~ ) P ~ ( P R ~ ) ~ . give a I.1-vinyl species but reaction with HBF4 gives the W=Pt tungsten-alkene complex [Cp(OC) (C2H4 )W(p-CO) 2Pt ( PR3 1 2]+. this reacts with NaBH4 to give a p-CHMe complex.239 CH2N2 to Cp(OC)2W(p-Ctol)Fe(CO)3 results in addition of one or two CH2 groups across the M-M bond, according to the reaction conditions, resulting in U-vinyl Complexes - 240 The action of heat

on ( 3 8 ) (R = H, But; M = Mo, W ) gives (39).241,242 Addition of hydrogen to (39; M = Mo) causes formation of the ,,-alkylidyne ( 4 0 )

in a reaction reversed by heat.242

with LiCCPh affords the This reacts with MeS03CF3 or MeOH to

the neutral Mo2 (C0)q (p-n2-CCRPh)Cp2 (R = Me or HI. These

(p-n 2-CHCPhCH2 )Cp2 (R = Me). 234 The p-alkyne

A minor product of the reaction

A review article illustrates the use of W(C0)2(CR)Cp as

Addition of Pt(C2H4) (PR3)2 to W(C0)2(CMe)Cp gives the This compound methylates to

In turn, Addition of

The terminal alkylidyne in M[Re(CO)5](~~)4(c~) (M = Cr, Mo, W; R = tol, Me) transforms to I.1-alkylidenes, 1.1-vinyls, and 1.1-acyls.~~~ The reaction between Fe2(coI9 and M[Re(C0I5] (C0)4(Ctol) proceeds directly to p-alkylidynes ( M = Cr) but (41) for M = Mo and W.244 Protonation of Fe2W(P-CO)(~-~iOI( 3-Ctol)(CO)6Cp by HBF4 leads to Fe2W (1.1 -Ctol) (p 3-NOH 1 ( CO )7Cp. 245 The reaction between F ~ ~ ~ ( P - C O ) ( P ~ - C ~ O ~ ) ( C O ) ~ C ~ and W(C0)2(Ctol)Cp gives W~(C0)4(p-tolCCtol)Cp2 as major product but three cluster species are produced in the analogous reaction using W(CO)2 ( C M ~ ) C P . ~ ~ ~ Addition of PR2H to Fe2W(p-CO) (p3-Ctol)(CO)gCp gives p2-CR species that convert to 1.1 3-CR derivatives on thermolysis. 247 The reactions

of PR2 bridged I.13-alkylidynes Co2W(u-H) (P3-Ctol) ( -PR2)(C0)6Cp ( R =

Ph, Et) with PHR'2 (R' = Ph or Et) or R"CCR" (R" = Me, Et) are dominated by processes involving P-C, C-C, and C-H bond formations.248 The reaction of C O ~ M ( C O ) ~ ( V ~ - C R ) C ~ (R = Me, Ph,

Complexes Containing Metal-Carbon o-Bonds (Sc to Mn) 25 1

COPh, etc.) with [Ni(CO)Cp]2 (M = Mo, W) leads to COMN~(CO)~(~~-CR)CP while the corresponding reaction with [ Fe (CO) ] 2- yields FeCoM(H) (CO) 8 (11 3-CR )Cp. 249

reactions such as that of M[Re(CC)5](co)4(Ctol) (M = Cr, W) with Pt (C2H4 Related reactions of Pt(C2H4)3 with W(C0)2(CR)L ( L = Cp, R = Me, Ph; L = Cp*, R = Me, Ph, toll give PtW2(C0)4(p-CR)2L2 while the corresponding reactions with Ni(codI2 give the analogous nickel species. occur to tetra- and pentanuclear clusters.251 P ~ W ~ ( C O ) ~ ( U - C P ~ ) ~ C P ~ with Ni(cod12 gives Ni2Pt2W,(CO)8(u3-CPh)4cp4 and Ni2PtzW4(v2-CPh) (113-CPh)3(CO)8Cp4 containing rings of eight metal atoms.252 W(C0)2(CR)Cp provides the seven metal chain complex P t 3 W 4 ( p - C R ) , ( p 3 - C R ) ( C O ) g C p q which in turn reacts with Pt(C2H413 to give an eight metal ring complex (43).253 The reaction of w2 ( OCH2But) 6 ( py) 2 with RCCR gives W3 ( OCH2But g (P 3-CR ) in reactions whose rates vary in the order Et = Ph > Me. The alkylidyne W(OBut)3(CMe) carbonylates to form W2(OBut)6(C0) (P-MeCCMe) 0254

A number of pentanuclear metal complexes are available by

or Ni (cod ) 2 which provide ( 42 1 . 250

Further reactions Reaction of

The reaction of Pt3W2(CO)4(cod)2(v3-Ctol)Cp2 and

6. Group 7 (Mn, Tc, and Re)

There is material of relevance in reviews on manganese255, rhenium, 256, the reactions of manganese atoms in methane matrices, 257 and the chemistry of ReCp* 0x0 complexes. 258

Addition of MnRX, MnR2, LiMnR3, XMgMnR3 ( R = alkyl, Ph) to cyclohexenone generally results in 1,4 addition and B-reduction products in various yields according to the reaction conditions. 259 A review on sterically hindered organosilicon chemsitry mentions the reaction of anhydrous MnC12 with LiC(SiMe313 which affords the two coordinate Mn[C(SiMe3)3]2. 260

that the site of protonation of ReCl( q2-H2C=C=CHPh (dppe ) 2 which gives the n2-vinyl [ ReCl ( n2-CBzCH2 ) (dppe ) Treatment of fac-Mn(CCBut) (C0)3(dppe) with CuCl results in coordination of the a-CCBut function to CuCl in an n2-fashion.262

Theoretical calculations concur with experimental data showing

1' is the CHPh carbon. 261

Gas phase infra red spectra on various combinations of 2H and .- "C methyl substituted MMe(C0I5 (M = Mn, Re) show that all M-C bonds increase in strength on going from manganese to rhenium, and suggest a negligible trans effect for the methyl group.263 Photolysis of MnMe(C0l5 in methane or argon matrices results in


to\ I

Cp(0C

I to1

(42) M i N i , Pt

6 Mn (COIL

0 C

I ,/’ ,OH C0

Complexes Containing Metal-Carbon u- Bonds (Sc to Mn) 253

MnMe(CC)4 as two isomers, with the vacant site either to the methyl group.264 A thermochemical study shows that reaction Of A12Br6 with MnMe(C015 is exothermic by 22.2 f 0 .6 kcal m01-1-265 A theoretical study by Hartree-Foch-Slater transition state methods concerns the migratory aptitude of hydride or alkyl to XY in MnR(C0I4(xy) (R = H, Me; XY = CO, CS, Mass SpeCtrOSCOpiC studies show that the molecular ion of M ~ ( Q ’ - C ~ H ~ ) and Mn(n1-CH2CH=CMe2) (C0l5 loses carbonyl or allyl. release of selected metastable ions indicates r11-r13 rearrangements. 267

or trans

Kinetic energy

Studies on the reaction of Mn(C6~4~~e)-p)(~O)5 with e-MnH(CO)4(PMe2Ph) show the nucleophile promoting the initial insertion reaction, such as PPh30, dissociates prior to trapping by the final incoming ligand.268 Kinetic studies on reactions of EtRe(C0I5 and transition metal hydrides which give aldehydes suggest the mechanism in MeCN includes a step in which the hydride attacks intermediate Re(C0Me) (NCMe) (C0)q at the carbonylation reactions of &-MnMe(CO)4L with *-MnH(CO)qL [L =

CO, P(OPhI3, P(OMe)3, PBu3] show little dependence on L, suggesting the transition state has little u n s a t ~ r a t i o n . ~ ~ ~

Aryl C-H bond activation occurs in the reaction of Me(C6H4R)C”-N=C(CsH4R)Me (R = H, NMe2) with MnMe(C015 which monometallated or dimetallated products ( 4 4 ) .271 Addition of LiEt3BH to Mn[C(O)C(O)Ph)](CO)5 affords the metallacycle [ & - I { C ( O ) O C H P ~ ~ ( O ) } ( C O ) ~ ] - .

give Mn[C(O)C(OH)(Ph)Hl(CO)5 or Me3SiC1 to give Mn[C(0)C(OSiMe3) (Ph)H] (C0)5.272 CH2SiMe3, aryl) with Ph2PSiMe3 gives Mn[CR(OSiMe3)PPh2](CO)5. Passage of the CHzSiMe3 derivative through wet silica causes formation of Mn[C(0)CH2SiMe3] (C0)4(PPh2H) .273 MHR3 (M = Si, Sn; R = Bun, Ph) gives MeCHO and Mn(MR3)(C0)5 probably y& the oxidative addition of MHR3 and l o s s of a carbonyl ligand.274 - 0-C6H4(PPh2)(CH2SiMe2But) gives the chelated species R & [ C H ( C S i M e 3 ) ( C 6 H 4 ; P h 2 - O ) 1 ( C 0 ) 4 .

“Et4][F] to form the anion ( 4 5 ) which on treatment with Si02/H2O gives ( 46 1. 275 H~/co gives Mn ( C0013CH2tol ) (CO) 5 probably via an q2-aCY1 intermediate.276 ReH(COI5 the formyl [ReBr(CHO) (C0)41-. Oxidative addition of R3SnH to the formyl intermediate gives Re(CH)(H)(SnR3)(C0)3 the

This in turn reacts with CF3S03H to

Treatment of MnR(CO15 (R = Me,

Addition of excess

The reaction of ReBz(C0I5 with

This species further reacts with

The high pressure reaction of Mn ( 13COtol (CO 15 with

The reaction of ReBr(C015 with LiEt3BH gives


coordinatively unsaturated Re(CH0) (CO14. 277 Addition of PhN=C=NR to [Re(C0I5]- followed by acidification

gives [Re{=C(NPhI2} ( c o ) ~ ] ’ . ~ ~ ~ The reaction of [Mn(CO)5]- with C F ~ ( C O C ~ ) ~ leads to CF2[C(O)Mn(C0)5]2. Thermolysis of this Complex results in loss of CO to form M~[CF~C(O)M~(CO)~](CO)~ whose photochemical decarbonylation results in ( 4 7 ) . 279

Addition of Mr~(CBr~)(co)~ to [CO(CO)~]- gives the mixed metal

Treatment of ReBr2(o)Cp* with A1Me3 provides ReMe2(0)CpX and

ketenylidene [MnC02(co)~(p~-CCo) 1 - . 280

ReBr2(Me)2Cp*.281 CH2But, CHzCMe2Ph) leads to [ReR2(0) ( p - 0 ) 12. 282 and PPh3 to Re(0)3Cp* gives RLO(CMe=CMe-O-CMe=kMe)Cp*.z83

in the formation of benzyl isocyanate. Irradiation of ( 4 8 ) gives Mn(C0I2(thf )Cp’ along with N-benzylcarbamate.284 complex Mn ( q2-HCCC6H4CCH ) (CO) 2Cp on sequential treatment with PhLi and HC1 affords the vinylidene ( 4 9 1 , which in turn reacts with PPh3 to give ( 5 0 ) .285 Addition of Me2NS(0) (=CH2 )R (R = Me, Ph) to Mn(C0)2(THF)L (L = Cp, Cp’) provides [M~(CO)~LI~(P-CH~) and MII(,~-C~H~) (C0)2L.286

the subject of a theoretical study.287 Treatment of

The reaction of ReC13(0) (PPh3)2 with ZnR2 (R =

Addition of MeCCMe

Addition of BzN2 to Mn(C0)2(thf)Cp’ gives ( 4 8 1 , an intermediate

The n2-alkyne

The reduction of [Re(CO)(PPh3)(~o)cp]+ to ReMe(PPh3)(NO)Cp is

ReMe(PPh3) (N0)cp with HPF6.0Et2 gives the unsaturated pyramidal cation [Re(PPh3)(No)Cp]+ which adds aldehydes RCHO forming [Re( n2-RCHO) (PPh3) (No)cp]+ that are subsequently attacked stereospecif ical ly by D’ . 288 Molecular orbital calculations on the conversion of the cation [Re(CO) (PPh3) (No)cp]+ to the corresponding formyl suggests that the site of nucleophilic attack by hydride is the nitrosyl, and that the thermodynamically unfavourable M-NHO complex rearranges to the formyl Re(CH0) (PPh3) (NO)CP.~~’ Modifications in energy of the reaction coordinate diagrams on the reactions of R ~ ( C H ~ R ) ( P P ~ ~ ) ( N O ) C ~ (R = alkyl, Ph) with Ph3C+ which give [Re(=CHR)(PPh3)(~0)cp]+ are made on the basis of new data concerning the relative stabilities of the Re-C rotamers of the starting material. 290 Addition of MeSMe to [Re(=CH2) (PPh3 (NO)Cp]+ gives [Re(CH2SMe2) (PPh3 (NO)Cp]+. The SMez group is replaced on addition of any of PPh3, py, or SR-.291 On the other hand addition of PhIO to [Re(=CH2) (PPh3) (NO)Cp]+ gives [R~(T-,~-H~CO) (PPh3) (NO)Cp]+ presumably y& Re(CH201ph) (PPh3) ( ~ o ) c p ] + . ~ ~ ~ Re(CH20H)(CO)(NO)Cp with Zr(Cl)(Me)Cp2 gives Re[CH20Zr(Cl)Cp2](CO)(NO)Cp while that of Re(COZH)(CO)(NO)Cp with

The reaction of


/c5\

OC

B t I

(CO),

( 5 2 )

0 4 PPh -

Ph

I RelC0)4( PMe2Ph 1

// c\

Organometallic Chemistry 256 Zr(C1) (Me)Cp2 affords an n2-carboxylate species.293 Treatment of Re(COR)(NO)(PPh3)cp (R = H, Me, Bz, Ph) with LiN(CHMe2)z followed by Me1 gives ReMe(N0) (PPh3) [ n-C5H4(COR) 1 .294 Addition of BuLi/tmeda to [Re(CH2Pt~13)(PPh3)(~o)cp]+ results in loss of a methylene proton. alkylation to give [ [ ~ S , R R ) - R ~ ( C H M ~ P ~ O ~ ~ I ( P P ~ ~ ) ( N O ) C ~ ] + . ~ ~ ~

alkyl) to M ~ R ( C O ) ~ ( C ~ H ~ ) . the dienyl complexes Mn (CO) 2 ( PPh3 ) ( n5-CgH5R) . formation, the acyls Mn(C0R) (CO) (PPh3) (C6H6) are detectable. 296

Subsequent addition of MeS03CF3 results in stereospecific

The anion [Mn(CO)2(~s~6)]- is alkylated by various RX (R =

Prior to their These species react with PPh3 to give

Addition Of MeLi to MnBr(C0)2(C6Meg) or Me1 to [Mn(C0)2(C6Me6)]- gives klMe(C0)2(C6Me6), while addition Of MeLi to MnI(C0)2(C6H6) gives MnMe (co) 2 (C6Hs ) . 297

Cocondensation of rhenium atoms with arenes gives p-alkylidenes, such as (Ar)Re( u-H)2(p-CHPh)Re(Ar) in the case of toluene.298 The reaction of rhenium atoms with benzene and 1,5-cod leads to Re( q5--COd) (C6J36) and RePh(n4-cod) (C6H6) .299 agents PhLi, MeMgBr, C2H3MgBr,

Addition Of alkylating

or EtMgBr to ReI(PMe3)2(C6H6) results in the appropriate ReR(PMe3)2(~6~6). The phenyl species is also accessible as a minor product in the reaction between rhenium atoms, benzene, and PMe3 while the ethyl derivatives reacts with

[ Ph3C ] + to form [ Re ( n2-C2H4 ) ( PMe3 ) 2 ( C6H6 ) + . Photolysis of Re(N2 ) (PMe3 ) (CO)Cp* in the presence of benzene

gives the isolable ReH(Ph)(C0)(PMe3)cp* which on reaction with

CHBr3 gives Re(Br)2(CO) ( P M ~ ~ ) C P * . ~ ” in the presence Of a mixture Of C ~ H ~ and an alkane rsults in deuterium scrambling between C6H6 and the alkane, probably y& an intermediate Re(Hl2(~) (C6D5) (PPh3)cp,3O2 in the presence of benzene and cyclopropane gives a mixture of

ReH(Ph) ( P M E ~ ) ~ and ReH( q1-CHCH2CH2) (PMe3)zCp. arise in similar reactions involving hexane or cyclopentane.303

Photolysis of Re(H)2(PPh3)2cp

Photolysis of Re(PMe313Cp

Alkyl products also

Photolysis of Mn2(Co)10 in the presence of allene gives three dimanganese complexes including (51 1 . 304

(52) gives the vinyl (53).305 Photolysis of

Mn(CO)4(~-PPh2)(IJ-H)Mo(Co)2Cp in the presence of various alkenes gives the IJ-acyls C P ( O C ) ~ M O ( ~ - P P ~ ~ ) ( ) ~ R C O ) M ~ ( C O ) ~ whose IJ-COR group flips on carbonylation forming Cp(OC)2Mo( p-PPh2) ( p-COR)Mn(C0)4.306

The reaction of tran~-ReCl(CNSiMe3)(dppe)2 with HBF4 results in the carbyne [ReCl (CNH2) (dppe)2]+.307

Addition of PMe2Ph to

Complexes Containing Metal-Carbon 0-Bonds (Sc to Mn) 257

1. 2. 3. 4. 5. 6. 7. 8.

9.

10. 11. 12. 13. 14. 15. 16.

17.

18.

19.

20.

21.

22.

23. 24.

25.

26.

27. 28. 29. 30. 31.

32. 33. 34.

35.

36.

37. 38.

39. 40. 41. 42.

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286. E&r and E. Lucke, Orqanmeta l l ics , 1986, 5, 2114. 287. R.F. Fenske, M.C. M i l l e t t i , and M. Arndt, O r q a n m t a l l i c s , 1986, 5, 2316. 288. J.M. Fernandez, K. Ekerson, R.H. Larsen, and J.A. Gladysz, J. Am. Chem.

289. R.F. Fenske and M.C. M i l l e t t i , O r q a n m t a l l i c s , 1986, 5, 1243. 290. S. Georgiou and J.A. Gladysz, Tetrahedron, 1986, 42, 1109. 291. F.B. McCormick, W.B. Gleason, X. Zhao, P.C. Heah, and J.A. Gladysz,

292. W.E. Buhro, S. Georgiou, J.M. Fernandez, A.T. Patton, C.E. Strouse, and J.A.

293. C.T. Tso and A.R. Cut ler , J. Am. Chem. Soc., 1986, 108, 6069. 294. P.C. Heah , A.T. Patton, and J.A. Gladysz, J. Am. Chem. Soc., 1986, 108,

295. G.L. C r o c c o and J.A. Gladysz, J. Chm. Soc., man. "n., 1986, 1155. 296. P.K. Rush , S.K. Noh, and M. B m k h a r t , Orqanawta l l ics , 1986, 5, 1746. 297. R.J. Bernhardt, M.A. Wilmth, J.J. W e e r s , D.M. Iabrush, D.P. Evans, and J.C.

298. M.L.H. Green and D. O'Hare, J. C h a . Soc., Dalton Trans., 1986, 2469. 299. A.E. Derane, M.L.H. Green, and D. O'Hare, J. Chem. Soc., Dalton Trans.,

300. M.L.H. Green, D. O'Hare, and J . M . Wallis, Polyhedron, 1986, 5, 1363. 301. A.H. Klahn-Oliva, R.D. Singer, and D. Sutton, J. Am. Chem. Soc., 1986, 108,

302. W.D. Jones and J.A. Maquire, Orqanmeta l l ics , 1986, 5, 590. 303. T.T. Wenzel and R.G. Bergman, J. Am. Chm. SOC., 1986, 108, 4856. 304. C.G. Kreiter, M. Leyendecker, and W.S. Sheldrick, J. O r q a n m t . Chem., 1986,

305. A.A. Koridze, O.A. Kizas, N.E. Kolobova, A . I . Yanovsky, and Y.T. Struchov,

306. T. Ad:tia, K. Hendrick, A.D. Horton, M . J . Mays, and M. McPartlin, J. chem.

307. n L . Ponbeiro, D.L. Hughes, C.J. P icke t t , and R.L. Richards, J. Chem.

8271.

894.

J. Or ancmt. Chem., 1986, 302, 235.

Soc., 1986, 108, 8268.

O r q a n m t a l l i c s , 1986, 5, 1778.

Gladysz, Orqanmeta l l ics , 1986, 5, 956.

1185.

H u f f m , Orqancanetallics, 1986, 5, 883.

1986, 343.

3107.

302 , 35.

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Soc., Chm. Camnun., 1986, 1206.

Soc., Chem. chnnm., 1986, 246.

12 Complexes Containing Metal-Carbon 0- Bonds of the Groups Iron, Cobalt, and Nickel

BY A. K. SMITH 1 Introduction, Reviews, and Articles of General Interest

The format of this chapter is similar to that used in previous years.

transition metal ions with organic molecules.' alkane C-H bond Reviews published in 1986 cover the gas-phase chemistry of

cleavage with transition metals ,' reactions of metal atoms with methane in low temperature matrices, the synthesis of organometallics by decarboxylation reactions, the organometallic chemistry of transition-metal porphyrin complexes, and the chemistry of saturated hydrocarbon-bridged dinuclear complexes. A book entitled "Organometallic Intramolecular Co-ordination Compounds", and a review of cyclometallation reactions involving nitrogen and alkyl, alkenyl, and benzyl carbon donors8 have been published. The plenary and section lectures presented at the 12th International Conference on Organometallic Chemistry (Vienna, September 1985) have been published.' The 300th volume of J. Organomet. Chem. is commemorated by a number of reviews by well- known organometallic chemists; many of these reviews are of relevance to this chapter." ruthenium, osmium, and iridium ,I1 and the role of electrophilic metal carbenes as reaction intermediates in catalytic reactions ,I2 have been reviewed. The reactivity of the ions Ru+. Rh', and Pd' with alkanes in the gas phase has been shown to be markedly different to that of their first row congeners.13

6

7

Carbene and carbyne complexes of

2 Metal-Carbon o-Bonds involving Group VIII Metals

2.1 The Iron Triad. - A correlation between the site of insertion of the gas-phase ions Fe+, Co+, and Ni+ into C-C bonds in alkanes, to give intermediates of the type R-M+-R' , with the ionisation potentials of the alkyl radicals formed when the C-C bond is cleaved, has been reported.14 The gas-phase chemistry of



Fe(C0);,4, CO(CO);,~, and Co(NO)(CO)- alkanes, !-alcohols, bromochloroalcohols, and chloroalcohols has

15 been investigated.

with a series of n-chloro- 1,2

Intra- and intermolecular oxidative addition reactions to the co-ordinatively unsaturated species [Fe(depe) 1 have been investigated. l6 ’ l7 Thus, in inert solvents, CFe (depe 1 I undergoes oxidative addition to a C-H bond of a methylene group of one of the depe ligand ethyl substituents, to give CFe(H)tCH(Me)P(Et)CH2CH2PEt2}(depe)l, which reacts with benzene to give =-EFe(H) (Ph) (depeI21 .l6The addition of ethylene to [Fe(depe) I yields the vinyl complex +-[Fe(H)(C=CH2)- (depe)21.f7 Similarly, irradiation of [Fe(H21 (dmpel2I in benzene gives a mixture of cis- and trans-[Fe(H)(Ph) (dmpe)2]; irradiation in cyclopentene gives =-[Fe(H)(cyclopentyl) ( d m ~ e ) ~ I ! and irradiation in alkenes CH2=CR1R2 (Rh=R2=H; R =H ,R -Pr’) produces - ci~-[Fe(H)(alkenyl)(dmpe)~I together with u-alkeneiron complexes .18 The photolytic dehydrogenation of the cis-dihydrides CFe(H)2(pp3)1 and [R~(H)~(pp~)1 Ipp3=P(CH2CH2CH2PMez)3} in benzene leads to intramolecular C-H activation for the iron comDlex to aive

2

1 2-

[F&{P(CH2CH2 CH2P(Me)tH2) (CH2CH2CH2PMe2)2 ’I activation for the ruthenium complex to give CRu(H) (Ph) (pp3) 1 .19

A number of compounds of the type [Fe(Cp) (C0)2(q’-C-ligand) 1 and its derivatives have been synthesised; such complexes include 2o CFe(Cp)(C0)2(Me)l by PPh3 abstraction from CFe(Cp)(CO)(PPh3)(COMd?, [Fe (Cp) (CO

and intramolecular C-H

(C (CF3 ) (OH ) 1 1 , ” , CFe{C5H4C (OH )RR1l (CO 1 (Bz ) 1 ( R = R 1 =Ph; R=H,R1=Ph) , 2 2 [Fe(C5H4CHO) (C0)2(Bz) 1 , ” CFe{C5H4C(0)C1)-

(CO) (Bz) 1’’ and its intramolecular acylation reaction to give

[Fe(Cp) (CO,,{~’~(g)-CH=CHCH CH2Mell and [Fe(Cp) (C0I2(CH=CH2) 1 from p-alkenyldi-iron complexes,35 CFe(Cp1 (CO) {P(OPhl31 (ql-R) I {R=CH(Me)C(NR)Me, CH(Me) (COMe) , CH2CfCMe} , 2 6 and [Fe(Cp)(CO)tP(OCH2CH2)2Nl(Ar)l (Ar=Ph o r C H Me3) by reversible aryl group migration from phosphorus to irzn?27 The synthesis and photolysis of [Fe(C5Me5)(CO)2(CH2CH2SiMe3)1 has been reported.’* to 1,3-dienes to give CFe(Cp) (CO)2(q1-2-alkenyl) J complexes indicate that a radical pair mechanism is involved.’’ complexes [Fe(q5-cycloheptadienyl) (CO) (L) (Me) 1 {L=CO, P(OPhI3} have been synthesised and their CO insertion reactions have been studied.30 The reactions of complexes of the type [Fe(Cp) (C0)2(RI 1 that have been reported include treatment with Ph3C”, 31

[Fe(C0)2(q5-C L- H COC6H4CH2) CFe(Cp) (CO)2(q 1 -2,4-pentadienyl)

CIDNP studies of the l,4-addition of [Fe(Cp) (C0)2H]

The

Complexes Containing Metal-Carbon o-Bonds (Fe, Co, Ni) 267

1 cycloaddition reactions involving [Fe(Cp) (C0I2(q -C5H5) 3 , 32 the photochemical conversion of CFe(Cp)(C0I2(q -C H 1 1 and related complexes to ferrocene and its derivatives, 335t:e conversion of [Fe(Cp) (CO) {P(OPh)3} {q1-C(R3)=C(R1)R2) 1 to iFe(Cp) (CO) tP(QPh)3]- {ql-C(0)C(R l=C(R1)R 1 1 induced by [Fe(Cp)21tBF41 or Ce(IV) under CO, 34 and insertion reactions of N-sulphinyl sulphonamides and sulphur bis(sulphony1imide) into the Fe-C a-bonds of CFe(Cp1 (C0)- (L) (R) j [R=Me, 35 q'-allyl, -propargyl, or -cyclopropylmethyl; L=PPh3, P(OPhI31, among other complexes. Methyl and phenyl shifts from the B - to the =-carbon atom of [Fe(Cp) (C0)2(2,2-dimethypropyl- idene)lCBF41 and CFe(Cp)(C0)2(2-methyl-2-phenyl-propylidene)~[BF4~ leading to the appropriate iron-02-alkene complexes have been ~bserved.~' Treatment of [Fe(Cp) (C0l2 (0'-1-bromoallyl) 1 or [Fe (Cp) (CO) ( q1-1-bromo-2-methallyl) ] complexes with CRZnCl1 (R=aryl or vinyl group) yields the [1,31 sigmatopic shifted condensation products [Fe(Cp) ( C O ) (q1-CH=CHCH2R) 1 and [Fe(Cp) (CO)2-

Ph)(C0)2Me] (R=H,Me) leads to the loss of either CO or methyl radicals; the CO loss product undergoes intramolecular oxidative addition to give [Frn5--C6H4 1 (CO) I , which is converted to [Fe(q5-C R CH2Ph) (C0)2H] by irradiation under H2 .39 Acylation of the metal anions [MLn]- [ML,=F~(CP)(CO)~, Mo(C~)(CO)~(PP~~), Ni(Cp) ('201, Mn(C0I5, or Co(Z0) (PMe2Ph) 1 by CFe(Cp) (C0)2(CH2COC1) 1 gives the heterobimetallic p-0'-ketene complexes [Fe(Cp) (CO) 2- (CH2CO)MLnl. 40 [Fe(Cp) (Co) (C Ph) 1 and [Co,(CO),l yields [Co2{p-q2-PhC2Fe(CO)2- (cp)l(co)61 (1). 2 4 1

1

3 2

36

tq1-CH=C(Me)CH2Rll respectively.3' Irradiation of [Fe(q 5 -C R CH - 5 4 2

5 4

-

The reaction between the a-acetylide complex

The reaction of electroceduced iron-porphyrin complexes with alkyl halides has yielded a series of iron(III), iron(II1, and iron ( I) alkyl porphyrin complexes. 42 studies of iron(II1) porphyrin complexes with axial phenyl or tolyl groups have been reported.

'H n. m . r . spectroscop%c

43

Using [{Fe(Cp)~co)~2(p-co)(p-CH3~l as a model, the electronic factors leading to the bridging of methyl ligands in dinuclear complexes have been investigated using Fenske-Hall M.O. calculat- i o n ~ . ~ ~ (p-q5:q1-6, 6-diphenylfulvene) 1(2) (M=Fe, Ru; L=C0,PR3 ,SbPh3,CH2- pphj,,c~-) has been published.45 N.m .r. studies of the complexes [M2(C0)5(L) tp-C(R)=C(R')COC(R' )=C(R)l 1 (M=Fe,Ru; LK0,PPh3,AsPh3, SbPh3; R=R'=Me,Ph) show that a fluxional process leading to exchange of Q - and x-bonds at the two metal centres is occurring?6

The synthesis of complexes of the type [M2(C0)5(L)-


Ph

( 3 )

( co

Br Ph

(5)

Complexes Containing Metal-Carbon a-Bonds (Fe, Co, Ni) 269

The complexes C(C0)3F:(p-PRz) (p-R28CH2)$e(CO)31 and C(C0I2Fe- (p-PR 2 ( p - R 2 P C H 2 ) ( p - R 2 P C H Z P R z ) F e ( C 0 ) 2 3 are produced on heating [Fe2(CO)7(p-R PCH2PRZ)I and CFe2(CO)5(p-R2PCH2PRz)1 (R=Me,Ph), re~pectively.'~ With [Fez(CO)71p-Ph2PCH(Me)PPhzl 1 , however, heating leads to P-C bond cleavage accompanied by ortho-metallation to give ( 3 .47 lithium followed by benzoyl chloride results in the formation of the benzoate-substituted ferrole complex ( 4 ) .48 A comparative n.m.r. study of binuclear complexes of iron, ruthenium, and osmium, containing a metallacyclopentadiene ring has been reported. 4 9

Treatment of [Fe3 (CO) 12 I with l-methoxyallenyl-

Alkyl-ruthenium and osmium complexes of general formula [MzR61,

(R=CHzSiMe3,CHzCMe3; R'=Me,Et; R"=Ph,SiMe 1 have been synthesised. [M2R4(02CMe)2J, [Ru2R4Ri2J, and CRu2(NR" )2(CH2SiMe3)61

The interaction of CRu R I with oxygen gives the ruthenium(V) oxoalkyls [R3Ru(0)Ru(O)R31, and the treatment of [ O S ~ ( C H ~ C M ~ ~ ) ~ - (p-02CMe)Z1 with [C3H5MgXl leads to the formation of [Os2 ( n3-C3H5) (CH2CMe3) 1. 50 The synthesis of the first ruthenium- (VI) alkyl complexes [Ru(N)R41-, C R U ( N ) M ~ ~ ( C H ~ S ~ M ~ ~ ) ~ I - , and CRu(N) (CH2SiMe3) (OSiMe3 1 1- (R=Me or CH2SiMe3 1 has been reported!' It has been shown by n.m.r. studies that, €or a wide range of ruthenium(I1) complexes containing a phenyl or substituted phenyl ligand, that there is a preferred orientation of that ligand and a significant barrier to its .rotation.52 - cis-dimetalla-alkene complex, [Ru(CO)2tC(CZCPh)=C(Ph)HgCl}Cl- ( PMe2Ph ) 1 has been determined .53,

THF and in cyclopentene affords [RU(H~(~HOCH,CH,&H,)IP(CH~CH~CH~- PMe2l3lI and ~ R U ( H ) ( ~ = C H C H ~ C H ~ ~ H ~ ) ~ P ( C H ~ C H ~ C H ~ P M ~ ~ ) ~ ~ I , re~pectively.~~ NazCRu(CO) 4 1 reacts with alkanediylbis( trifluoro- methanesulphonates), (YCHZCH2I2 and cyclo-C6H10(CH2Y)z (Y=CF3SOZO) to give the ruthenacycloalkanes, C(C0)4RLCH CHzCHzEHz3 and [ (CO) 4RkHZ-~y~l~-C6H10-kHz 1 , respectively. '!5 Thermolysis of CR~(drnpe)~(H)(naphthyl)I in the presence of 2,6-xylyl isocyanide results in the formation of the indole-ruthenium complex ( 5 ) .56 The complexes [RUR(CO)~( triphos) I + (R=Me,Et ,Bz,allyl).:have been synthesised by oxidative addition of the appropriate alkyl halide to [R~(CO)~(triphos) The alkyl complexes CRuR(C0I2(triphos) I+ react with isocyanides or phosphines to form chiral complexes of the type fac-[RuR(CO)L(triphos) 1' [R=Me,Bz; L=P(OMe) 3 , ~ ~ ~ ~ t , ~ ~ ~ u S J

of which the derivative with R=Me and L=CNBut has been isolated in

5 0 3

2 6

The structure of the

The reduction of [RuC12tP(CHzCHzCH2PMe2)3)1 with lithium dust in


an enantiomerically pure form .58 ruthenium complexes CRu(C5Me5)(CO)Z(CH20H)] and tRu(C5Me5)(CO)(L)- (CHO)] (L=CO or PMe Ph) have been synthesised and studied as models for intermediates involved in the reduction of CO to oxygenates.59 A ruthenium complex with a cyclooctadiene derived Q1-alkenyl ligand, [Ru(Cp)(LL^,)(1-u-C8H13)J ( LL-dmpe, dppm) has been synthesised.

The hydroxymethyl and formyl

2

60

The ruthenacyclopentatriene complex, CRuBr(Cp)(C4H2Ph2)l ( 6 ) has been synthesised and shown to undergo oxidative addition with donor ligands, L CL=P(OMe)3,PMe2Ph,morpholinel to give the ruthenacyclo- pentadiene complexes CRuBr(Cp) (L) (C4H2Ph2) 1 .61 u , q 3 ( 5e 1 -butadienylruthenium complex CRu(Cp 1 {=C (Ph 1 -q 3-C (Ph )C (Ph) - CH(Ph)}l with P(OMel3 gives the a , q (3e)-butadienyl complex [&u(Cp)lP(OMe)3}{C(Ph)=C(Ph)C(Ph)kH(Ph)ll which has been shown to undergo a zeta-hydrogen abstraction reaction. 6 2

Treatment of the

2

The ortho-metallated complex [RbCl (PPh3) {C6H3MeO; (OC6H4Me) 2} 1 has been prepared and shown to be a very active catalyst for alkene hydrogenation .63 complex Cku{P (0&6H3Me) (OC6H4Me-4 1 2)2 (C0l2 1 has been determined .64 Cyclometallated complexes of the type CRu( bipy ) cyclometallated ligands 2-(3-nitrophenyl)pyridine, phenylpyridine, benzoChjquinoline, azobenzene, or - p-(dimethylamino)azobenzenel have been prepared and characterised.

The vinylmetal complexes LM(CH=CHR)Cl(CO) (PPri)21 (M=Ru,OS;

The crystal structure of the cyclometallated

(L) 1+ [ L= the

65

R=H,Ph) are formed by alkyne insertion reactions of CMH(C1) (CO) (PPri)21.66 Treatment of the latter complex (M=Ru) with HCECPh and KOH in methanol affords a mixture of [Ru(CECPh)2(CO) (PPr;l21 and [Ru(CXPh) (CH=CHPh) (CO) (PPr;),] .66

[Ru(CO)C1(RC=CHR')(PPh3)21 (R=H,R'=C3H,,Ph; R=R'=Ph) have been synthesised by insertion reactions of the appropriate alkyne into the Ru-H bond in the complex CRu(CO)Cl(H) (PPh3)31.67 has been made of the Ru-C bonds in the acetylide complex CRu(C~CPh)(dppe)(Cp)l, the vinylidene complex CRu(C=CMePh)(PPh3)2- (Cp)I[Il, and the carbene complex [Ru{C(OMe)Etl(PPh3)2(Cp)l[PF61, by use of X-ray crystallography. 6 8 with [Li(C=CPh)l produces LRu (CECPh)(PhNpy)41, a diruthenium(I1, 111) compound with an axial qE-acetylide ligand.69 Carbene (N2CR2) addition to LRu2(CO)6(u2-q2-CXPh) (p-PPh2) 1 results in the formation of the p2-q2-allenyl complexes [Ru2 (C0l6 (p2-q2-R2C=C- =CPh ) ( p-PPh2 ) 1 (R=H ,Me, Ph 1 . 70 The heteronuclear ruthenium-phenyl complex [(dppm)(Ph)R~(u-Ph2PCH2PPh)(p-H)dh(cod)lhas been Prepared

The alkenyl complexes

A comparison

The reaction of [Ru2C1 ( PhNpy 3

Complexes Containing MetaCCarbon a-Bonds (Fe, Co, Ni) 27 1

71 and structurally characterised by X-ray crystallography.

prepared by treatment of [Ru(OEP)Br21 with RLi.72 conversion of [RU(OEP)(E~)~I to the ethylidene complex CRu(OEP)(CH- CH3)] has demonstrated the radical nature of the process, and the Ru-C bond dissociation energy in the bis(ethy1) complex has been calculated. 73

The porphyrin complexes [Ru(OEP)R21 (R=Ph or Me) have been A study of the

Treatment of [Os(N) (R)41[NBuyl (R=CH2SiMe3,CH2Ph,Me) with CMe303[BF41 results in the methylation of the nitrido atom to give [Os (NMe) (R) 4]. 74 silylimido complexes have also been carried out.74 molecular activation of C-H bonds in benzene, tetramethylsilane, and trimethylphosphine by complexes derived from =-COs(H)R- (PMe 1 (R=Me,CH2CMe3,CH2SiMe3) by thermolysis has been investigated. 475’76 A number of arene-osmium complexes containing 0s-C a-bonds have been isolated from reactions of 0s atoms with organic substrates; examples include [ {Os ( n6-C6H3Me3-1, 3,s 1 l 2 ( p - H )2-

{p-CH(C6H3Me2-3 , 5 1 1 1 , [ {Os(n6-C6H3Me3-l, 3,s) 12{p-CH(C6H3Me2-3 , 5 ) 11 , and [ {Os(q6-C H ) I3{p3-(CH2 1 3CH} (p-H) 1. 7 7

The f ive-membered osma-heterocycles , [PF6 I and c (C H )(PPri )OtsC(R )=C( I )C(OMe) =d 1 CPF6 1 (R=H, Me ,C02Me) have been ~ynthesised.~’ latter complex (R=H) indicates some carbenoid character of the 0s-C bond. 78 The four-membered osma-heterocycles, C (C H6) (CH2X )O(s{CH2- CH (Me) Per; 1 j [PF6 1 (X=H ,D) have been synthesised. ” Thg metalla- cyclobutan-3-ones, [ O ! S { C H ~ C ( O ) ~ H ~ ) ( C O ) ~ ( P P ~ ~ ) ~ I , ~ I ~ { C H ~ C ( O ) ~ H ~ ~ C ~ -

(CO)(PPh3)21, and rP;{CH2C(0)EH2)(PPh3)21 are formed on treatment of the silenol ether CH2=C(OSiMe3)CH2C1 with COS(CO)~CPP~~)~I, [IrH(CO) (PPh3l31, and LPt(trans-stilbene1 (PPh3I23, respectively.80

The alkyl substituted triosmium cluster C O S ~ ( C O ) ~ ~ ( M ~ ) ( p - 1 1 1 has been synthesised and shown to react with CO to give a mixture

Alkylations to give ethylimido and trimethyl- The inter-

Treatment of COs(q6-C6H6) (z4:C6H6) 1 with PMe3 gives COs(n6-C6H6) (PMe3) (PhIHI. 77

( C6H6 ( PPr; ) dsCH=CHC (OMe) =b 1 6 6

The short (202pm) 0s-C distance in the

- ’

of the ql-acetyl derivative and (in small amounts) the p-acetyl cluster COs3(CO)10(p-O=CMe) ( p - I ) 1 .81 The ethyl substituted cluster [OS~H(CO)~~(E$))I undergoes = , B , and reductive elimination processes leading to LOS~(H)~(CO)~~(CHCH~)I, [OS~(H)~(CO) and C2H4,and cOs3 (HI (CO) (CHCH2 1 3 and ethane, respective1ytd2 The reaction of maleic anhydride with COs3(H)2(CO),o(NC0)3’ affords a cluster containing a a-bound succinoyl anhydride ligand, (NCO)(a-succinoyl)]-, which has been characterised by X-ray crystallography .83

[OS~(H)(CO)~-

The oxidative addition of CAu(CECPh)LI

272 Organomeiallic Chemistry

(L=PPh3 or PMe2Ph) to [os3(CO),o(MeCN)21 affords the doubly- bridged phenylethynyl triosmium cluster [0s3 ( p , q2-C,CPh) (p-AuL) - (CO)lol which decarbonylates in refluxing heptane to produce the triply-bridged phenylethynyl ccmpound COs3 ( p3, q2-C5CPh) ( p-AuL) -

84 (co).9j. 2 .2 The Cobalt Triad. - The complex CCo(l-norbornyl)4)] has been shown to be a low-spin tetrahedral complex by a combination of - X-ray crystallography and magnetic susceptibility measurements. A series of ( Q -benzyl) - , ( q3-benzyl) -, and ( 0’-phenylacetyl) - cobalt carbonyls have been synthesised. Alkyl-CO insertion reactions of [CO(CO)~(PP~~M~)R] (R=Me,CH20Me,CH CO Et) and [Co(CO)2(PPh2Me)2(CH20Me) 1 have been in~estigat:d.*~ Treatment of CCO(C~)(CO)(I)~I with [(CF3)2Cd.glyme1 affords [CO(C~)(CO)(CF~)~] and [Co(Cp) (CO) (CF3)Il -88 The reaction of the bistrifluoromethyl complex with CMe2Cdl results in the formation of CCo(Cp)(CO)- (Me)2] .88 gives the chloromethylcobalt complex, CCo(C5Me5)(CO)(CH2C1)Cll. The oxidative addition of aryl halides, ArX, to [ C O ( P P ~ ~ ) ~ ( M ~ ) ] yields both ArAr and ArMe (Ar=4-MeC6H4), but exclusively ArMe when Ar=l- and 2-bromonaphthalene and 4-bromobiphenyl . The inter- ference of the decomposition of the triphenylphosphine ligand in these reactions has been studied.” alkyl carboxylates into the Co-methyl bond in [Co(PPh3I3(Me)3 has

been investigated. 91 ethylcobalt complex [Co(C5Me5) (Et) (PMe2Ph) 1’ have provided evidence for the processes involved in the interchange of the ethyl protons. These processes are Co-H cleauage/methyl rotation (the complex contains a M-H-C interaction), inversion of chirality at cobalt, and 6-elimination/alkene rotation.” the activation parameters of Co-C bond homolysis and the bond dissociation energy has been made by measurements of thermal racemisation rates of chiral alkylcobalt complexes. 93 Evidence has been presented for a single-electron-transfer activation in the cleavage of Co-C bonds of alkylcobalt (111) complexes with iodine. 94 arrangement v& a radical chain process to the complexes [Co- ( salen 1 ( py) ( C H 2 w C H 2 1 I . 95 as [Co(salen)(R)I have been synthesised by the oxidative alkylation of the corresponding cobalt(1) complex with various hydra- zines (RNHNH~).

85

1

The photolytic reaction of [Co(C5Me5) (CO)2] with CH2C1 89’

The insertion of aryl and

Spectroscopic and theoretical studies on the

An estimation of

The complexes [Co ( salen ( py ( 5-hexenyl) 1 undergo re-

Organocobalt ( I11 complexes such

96

Complexes Containing Metal-Carbon o-Bonds (Fe. Co, Ni) 273

Alkyne (HCZCC02Et) insertion into the Co-H bond of the complex [Co(np3)H1 Cnp3=N(CH2CH2PPh2)31, followedby the addition of NaBPh affords the a-alkenyl complex, CCo(np3)tC(C02Et)=CH2}l CBPh41. Oxidation of an aqueous solution of CCo(dacoda)(H20)l (dacoda=1,5- diazacyclooctane- N,N'-diacetic acid) to CCo{dacoda-C(2 1 1 ( H Z O ) 1 17) proceeds via an intermediate containing an agostic interaction. The synthesis of the three- and five-membered phosphacobaltacyclo-

974 '

98 - alkanes, [~C0)3CoPPh2CH21, C(C0)3CbPPh2(CH2)2;H21, and [ (C0l3- CbPCy2(CH ) dH 3 , and their reactions with CO and PPh3, have been re orted 492 TEe cobaltacyclopentene complexes [ (Cp)LCL{C(=NRj)C-

or a ( = N R 3 ) ) 1 (R 1 =Ph; R 2 =Ph or C02Me; R 3 =Ph,2,6-Me C H 2 6 $An

4-MeC H 1 have been prepared and structurally characterised.Luu The regioselective pre aration of the 4-iminocobaltacyclobutene

Ph,C02Me, or CN; R3=Ph,4-MeC6H4, or 2 ,6-MezC6H3), and their structure determination by X-ray crystallography, have been published .lo1 "02 The heterometallic (Co, Mg) dinuclear complexes [(Cp)Co(C2H4) (R)MgBr(TMED)] (8) (R=Ph,Me), in which the cobalt is a-bonded to the carbanionic R group, have been synthesised.lo3

Full details of alkane C-H bond activation by [Rh(C5Me5)(PMe3)j have been published .lo4 When CRh (C5Me5) (PMe3 1 is generated in mixtures of linear alkanes, only the products of insertion into primary C-H bonds are observed. However, evidence is presented to support the suggestion that insertion occurs into all the C-H bonds of the alkane, but the secondary insertion products rearrange, q2-C-H alkane complexes, into the primary products. A mechanistic study of the rearrangement of [Rh(C Me )(L)(cyclo- propy1)Hl (L=PMe3) to the rhodacyclobutane [(C5Me5) (L)RhCHzCH2CH21, and a new method of synthesis of the rhodacyclobutane complex, has been reported. lo5 bonds by the rhodium intermediate [Rh(C5Me5)(PMe3)] have been investigated.lo6 and CRh~CSMe5)2(C0)z(R)(R')1 (R,R'=Me,Et,Ph) have been synthesised by alkylation of the radical anion CRh(C5Me5)(C0)li or the dianion [Rh(C5Me5)(C0)J:- , or by the addition of RLi across the Rh=Rh double bond of [Rh(C5Me )(CO)12 followed by treatment with alkyl - p-toluenesulphonates. lo' The ligand (CO or PPh3) induced fragmentation reactions of the dimethyl derivative has been investigated!" C-H and Si-H bond activation is observed on photolysis of CRh(Cp)- (C2H4)(CO)I in low temperature matrices and in solution.

6 4

complexes [ (Cp) ( P P h 3 ) C ~ ~ C ( R 1 ) = C ( R 2 ) ~ ( = ~ R 3 ) 11 (R1=H,Me, or Ph; R 2 =

104

5-

Isotope effects in the activation of arene C-H

The dinuclear dialkyl complexes [Rh(C5Me5) (CO)R12

Thus, for


H ( 9 ) ( 1 0 )

0 L 11

L / ‘Ni’a F


example, prolonged photolysis of [Rh(Cp)(C H )(CO)] in a methane matrix at 20K yields ERh(Cp)(CO)(Me)Hl. 108'

Treatment of [RhBr(Me)(CH20Me)(PMe3)21 with Me3SiBr results in the formation of ethylene, formed by C-0 bond cleauage and methyl migration to a methylene group followed by 8-elimination. log The cationic compounds CRh(Me)(CH20Me)(PMe3)n(CH3CN)4-nJtSbF61 have a1 so been prepared. log The hydroxyacetyl complexes, [MCl(H) EC(0)- CH20H ( PMe3 1 ( M=Rh , Ir) have been prepared and the thermolysis of the rhodium derivative, which produces formaldehyde, and of its structural isomer, the carbomethoxy complex CRhCl(H){C(O)OMe)- ( PMe3 1 1 , which gives methanol, have been studied .lll

(R=OPh, 112Ph,C6H4C1 ,C6H40Me113 1 has been studied. addition of methyl-iodide or -bromide to the metal amide complexes [M(C8H14) tN(SiMe2CH2PR2I2 )I (M=Rh or Ir; R=Ph,Pr') produces CM(Me)- XIN(SiMe2CH2PR2)211 (X=Br,I), which reacts with CO to give CM(C0)- (Me X IN ( SiMe2CH2PR2 1 1 1 The cyclenphosphorane rhodium complex -LRhC1(PPh3) (cyc1enPH)I undergoes a three-fragment oxidative addition of CH2C12 to give the complex (9).

q-C8Fa) ( PMe3 1 1 provides the first example of a 1,4-n-COT ligand Protonation of the alkyne complex CRh(Cp) (PhCXPh) (PPr:) 1 with CF3C02H affords the vinyl complex [Rh(Cp) { (E)-C(Ph)=CHPhI (PPri)- (OCOCF3)l which has been converted to the metallaindene complex [ (Cp) ( PPri RhC6H4CH=CPh] .ll' complex CRh2(0 CMe)31PPh2(C6FsBr)lt(C6H4)P(Ph)(C F4Br))l has been synthesised .I1' The rhodacyclobutane complex Cd (CH2CMe2tH2 - (C5Me5)(PPh3)l and the dialkyl derivatives CM(CH2SiMe3)2(C5Me5)- (PPh3)1 (M=Rh,Ir) have been prepared. '19 iridium complex leads to the formation of the iridasilacyclobutane [I:(CH2SiMe2EH2) (C5Me5 (PPh ) 3 complexes of the types CM(C6H4PPh2)(CH2SiMe3)(C5Me5)1 (M=Rh,Ir), CRh(CH2CMe2CH2)(C5Me5)(PPh3)1, Ch(C6H4;Ph2)(CH2CMe3)(C5Me5)l (M=Rh, Ir) have been reported.l2O have been prepared by the insertion of [RhC1(C2H4)212 into an unstrained C-C bond where one of the carbon atoms is a chiral centre. Thus, for example, insertion into (?)-8-quinolinyl =-methoxybenzyl ketone gives a chloro-bridged polymer that reacts with pyridine to give [RhCl{CH(OMe)Ph) (py) (NCgH6C(0) 1 3 .121

the ylide complex [RhC13(DMSO)2(r11-cH CH=NEt )].I22

The oxidative addition of methyl iodide to CRh(acac1 (CO) (PR3)l The oxidative

115

The octafluorocyclooctatetraene rhodium complex [Rh(C5Me5) (1,4-

b - The ortho-metallated dirhodium

Thermolysis of the

A number of cyclometallated _3' -

Rhodium-chiral alkyl complexes

Treatment of mer-[RhC13(DMSO)31 with NEt3 produces isomers of

2 2


The rhodium(1) macrocycle[Rh(PPDOBF2 )I (PPDOBF2=[difluoroi~,~’- bis(3-pentanon-2-ylidene)-1,3-diaminopropane~dioximato~boratel~ acts as a s t a g nucleophile towards alkyl halides and may also be alkylated by its rhodium (111) alkyl halide adduct .123 of alkyl exchange between the rhodium(1) and rhodium(II1) complexes, lZ3 and the mechanisms of oxidative additions of alkyl halideslZ4 and organic d i h a l i d e ~ ’ ~ ~ to the rhodium( I) complex have been investigated. The organorhodium porphyrin complexes, [Rh- (TPP)R] (.R=formyl, hydroxymethyl, alkyl) have been prepared, and the photoinduced insertion of CO into the Rh-Me bond has been described. 126 H40Me,C6H4Me,C6H4C1) are prepared by treatment of CRh(OEP)Cl] with AgC104 or AgBF4 in the appropriate aromatic solvent.

M.O. calculations on the system [Ir(Cp) ( L ) (C2H4) 1 (L=phosphine) show that, in agreement with experiment, the q2-alkene complex has a slightly lower energy than the vinyl hydride complex. 128 vinyl hydride complexes, [ Ir (Cpl (L) ( t11-C2i-13 1 (H 1 3 ( L=C2H4, CO) in low temperature matrices, and L=C2H4,PPh3,DMS0 in solution) are formed on photolysis of CIr(Cp) (C2H4l21 .I2’ complex (L=C H undergoes secondary photolysis in matrices to give the vinylidene complex C(Cp)Ir(=C=CH2) (HI2]. 12’ When a solution of CIrCl(cyc1ooctene) l 2 and PPri in benzene is heated to 80C, a mixture of CIrCl (HI (PPrt) I andCIrC1 (H) (Ph) ( PPri l 2 1 is formed,

130 demonstrating intermolecular C-H bond activation of benzene. The iridium alkyl complexes C Ir (R 1 (dppe 3 I (R=Me, q1-C5H5 ) have been prepared. 13’ CIrH(Me) (PMe3)1 (Cy=cyclohexyl) has been prepared and characterised by - X-ray crystallography .132 olysis of this complex in benzene to give CIr(C5Me5)H(Ph) (PMe3) 1 have been investigated, and, in addition, the following trend in solution phase Ir-C bond dissociation energies has been established : phenyl >> n-pentyl > 2,3-dimethylbutyl > cyclopentyl .. cyclohexyl > neopentyl. 13’ [SbF61 {L=P(p-FC H 1 1 reacts with 1,l-dimethylcyclopentane to give first [Ir(5,5-C5H4Me2)L21[SbF61 and then [(MeC5H4)Ir(Me)L21 CSbF61 .133

cleavage have been investigated. 133 An investigation of the rearrangement of the - sec-alkyliridium(II1) complexes cIrYI(E-R)- (COIL2] (Y=Cl,I; L=PMe3,P14e2Ph) to the n-alkyl isomers has been

The kinetics

The arylrhodium complexes iRh(0EP) (Ar) 1 (Ar=Ph,C6-

127

The

The vinyl hydride

2 4

The methyl derivative reacts with acid to form cis- The alkyl iridium complex [Ir(C5Me5)H(Cy)-

The kinetics and mechanism of the therm-

The iridium complex [ Ir ( H 1 ( Me2C0 1 2L2 I

- 6 4 3

A number of similar transformations involving C-C bond


made. 134 been synthesised, and the methyl derivative converted to [Irx(Me)- ( R I 1 (CO) ( PMe3 1 1 ( R =Prn, P F ~ , Bun, BuSeC ,m-pentyl ,CH (Me )CH2CH2Me) by oxidative addition of the appropriate alkyl halide. 135 The oxidative addition of functionalised alkyl bromides, RBr (R=CH2C02Et, MeCHC02Et,MeCHCOMe,EtCHN02) to [IrC1(CO)L21 (L=PMe2Ph,PMePh2,PMe3) gives rise to the iridium(II1) complexes CIrBrC1(R)(CO)L2], which do not undergo E - a l k y l to n-alkyl i s ~ m e r i s a t i o n . ~ ~ ~ octadienyl hydride complex, ~-CIr(H)(a-C8Hl,)(np3)l {np3=N(CH 2 - CH2PPh2l31 is formed on.treatment of CIr(np3) 1' with 1,5-cyclooctadiene. 13' CSbF61 readily undergoes MeCN displacement reactions to yield a variety of related complexes.

Cyclometallated complexes of iridium that have been reported include [?rH(Cl) (CH2CMe2'1PBui) (PBu:) 1 ,I3' CIFH(C1) (CH2SiMe2CH2bBu:) - (Bu:PCH,SiMe,) [ I ' r t G e C l ( N R , ) N ( R ) S i M e , E H , ) ( C O ) , H t G e ( N R , ) " } ]

The complexes [ IrR (CO) (PMe3 ) , 1 (R=Me ,CH2SiMe3, Ph have

The a-cyclo-

The cationic complex [Ir(CF3)C1(MeCN) (CO) (PPh3l21

138

r (C6H4C (0)CC (Ph )ObPh2 1 ( PPh3 1 , 1 .14'

C(p-Cl)x(~-Br)3-xRe2(CO)6]- (x-1.5) is obtained from the reaction of CIr(C5Me5) (COT2], [Re(C0)4Br12, and CH2C12. 142 The iodomethyl complex, [Ir2(CO)4(p-pz)2(I)(CH21)], is the major product of the reaction between CH212 and CIr(C0)2(p-pz)12 (pzH=pyrazole). With 1,3-C3H612, CIr(CO),(p-pz)I, reacts to give the iodopropyl complex CIr, (CO) ( p-pz) 2I (CH2CH2CH21) 1 .143 The preparation and some reactions of the dinuclear complex C(C5Me5)(Ph)Ir(p-H)- ( p - q ' , q3-CHCHCH2 ) Ir (C5Me5 1 I have been reported. 144 iridium heterobimetallic complex, C(CO)4W(p-PPh2)21r(Me)(COD)l has been synthesised from [IrC1(COD)I2 and CW(C0)4(PPh2H)21, by treatment with BunLi and then methyl iodide.145

The chliromethyliridium complex, [ (C5Me5) Ir (C0l2 (CH2C1]+

143

The methyl-

The iridium(I1) porphyrin complex [Ir(OEP) 1, has been prepared and shown to undergo oxidative addition of H2 and alkyl C-H bonds, and alkene insertion reactions. 14' structural study of [Ir(OEP)(C H13)] [C8Hl3=a-cis-bicyclo(3.3.0)- - oct-1-yll has been reported. 2 . 3 The Nickel Triad. - The two isomeric organonickel(I1) complexes, trans-[Ni{CC1=CC1(C6H4Y)ICl(PMe3),1 and trans-[Ni{C(C6- H4Y)=CC12}C1(PMe 1 1 are formed on photolysis of trans-[Ni- CC1=CC12)(C6H4Y)(PMe3)21 (Y=Me,C1). 148 the type [Ni(Cp)(Me)(alkene)] has been prepared by treatment of

An electrochemical and

147

3 2 A series of complexes of


nickelocene with methylithium in the presence of alkene. 14' oxidatively induced decomposition of tran~-[NiRR'(L)~l (L=PMe Ph,

150 PEt3,bipy; R,R'=aryl or vinyl groups) has been studied.

are formed on oxidative addition of diaryl sulphides to Ni- (WU:),.~~' (PEt3I2] and c&-[Ni(Ar)(SAr')(dmpe)l undergo exchange to give a mixture of [Ni(Ar') (SAr)L21 and tNi(Ar)(SAr')L21. takes place y& reversible reductive elimination and oxidative addition of diaryl ~u1phides.l~~ (R=Et,Bun), CNi(PPh3l41, or [Ni(C2H4)31 + TMEDA, with cyclo- propabenzene results in the formation of the nickelacyclobuta- benzene derivatives (10). 153 The complex (10) reacts with C02 to f orm the six-membered carboxylate (11). 153 pentene complex, [(Me3P)2Ni(CH2CMe2-o--(!6H4) 1 has been synthesised and shown to undergo an insertion reaction with CH20 to give an oxynickelacycloheptene complex .154 The 2,3,4,5-tetraphenylnickel- ole complexes, [Ni(C4Ph4)(PPh3)21 and Cu(C4Ph4)(dppe)3 have been ~ynthesised.'~~ trimerisation of diphenylacetylene, and this aspect of the chemistry of nickel has been reviewed. 15' The complex CNi(C2H4)31 reacts with 7,7-difluorocyclopropabenzene in the presence of tetraethylethylenediamine (TEEDA) to give the nickelacycle (12) +56 Styrene undergoes a 1:l oxidative coupling reaction with C02 and

INi(~od)~l to give the oxanickelacyclopentanone complexes, [(cod)- I 1 f NitCH(Ph)CH2C(0)O)l and C(cod)Ni{CH2C(Ph)HC ( O , b } l , from which cinn- amic acid has been produced. 15' With ethylene and C02, [Ni (cod) 1 reacts to form oxanickelacyclopentanone and oxanickelacyclo- heptanone complexes, and n-pentenoic acid Azanickelacyclo- pentanones of the type C(bipy)Ni{CH(R)CH2C(0)N(Ph)}l, on treatment with oxidising agents such as CFeCl3I or 12, give either unsaturated acid amides or a,w-diacid amides by intermolecular e-C bond formation .I5'

The

Products of the type [Ni ( Ar ) ( SAr ) ( PBu:) 1 ( Ar=p-MeOC6H4, C6F5

The aryl groups in the complexes trans-[Ni(Ar) (SAr' 1 -

This process

Treatment of CNi(cod) (PR3l21

The nickelacyclo-

The former complex acts as a catalyst for the

r I

The metallathietane-3, 3-dioxidesI [h{CH(Ph)S(0)2?H(Ph) lL23 (M=Ni,Pd,Pt; L=AsPh3,P% ,3Et2) are formed on treatment of cis- or

trans-CMCl2LZ I with [PhCHS(0)2CHPh12-.160 The arylmetal complexes CNi{C6H3(CH2NMe2) -o,g')X21 (X=NO 3 ,NO2) ,161 "i{C H3(CH2NMe2)2- - ~,o'l(NCS)~(py) J:"-and [M{C6H3(CH2NMe2)2 ~ , ~ 1 1 ( ~ e - S 0 2 ) l have been reporte8: The nickelasilacyclobutene complex (13 1s formed on reaction of LNi(PEt3I4l with l-mesityl-3-phenyl-l,2-bis(trimethyl-

-


163 sily1)-1-silacyclopropene. The mechanism of the formation of the alkyl nickel(I1) complexes

CNiR (tmc) I + ( tmc=l, 4,8,1l-tetramethyl-l, 4,8,1l-tetraazacyclotetra- decane; R=primary alkyl) by reaction of CNi( tmc) 1' with alkyl halides has been investigated ,I6* and their reactions with alkyl halides to give [Ni( tmc) 12+ and RR' , RH, and R(-H) water to give LNi(tmc1 (OH1 1' and RH166 have been studied.

and with

Ab initio calculations have been carried out on complexes of the types CM(R2)L21 Me; L = phosphine) in order to investigate reductive coupling. Reductive elimination from CPd(Et)2(bipy)] in the presence and absence of additives has been studied.16' reaction between trans-CPd(m-tolyl)2(PEt2Ph)21 and MeI, which yields mainly E-xylene, has been suggested to involve a reductive elimination process with intermolecular exchange of organic groups. 16' been synthesised by the oxidative addition of Me1 to CPd(MeI2- (bipy ) 1 . The palladium ( IV 1 complex reductively eliminates ethane to form [Pd(Me) (bipy)II .170 The geometries and energetics of the species cis-CM(Me)2(PP3)21 ( M = Pd,or Pt) have been investigated, and the X-ray crystal structures of the PR3=PPh2Me derivatives have been determined.171 '172 igation of the carbonyl insertion reaction of [M(Me) (HI (CO)(PH3) I (M = Pd or Pt) shows that the reaction proceeds via methyl group migration. 173 The decomposition of alkylpalladium complexes that lack accessible B-hydrogenatoms, trans-CPdlPPh3),C1(R)J (R = Bz, CH2C6H4Me-g) occurs by various radical and non-radical routes depending on the alkyl group, the nature of the complex, and the reaction conditions .174 CCH(OMe)CMe2CH SMel)21 has been synthesised and its decomposition investigated. The q1-C5H5 complexes [M(C6H4N=NPh) (ql-Cp) (PEt3)21 (M = Pd,Pt)

The a-alkenyl complexes, trans-[MBr{C(C10H7)=CMe2)-

167 and CM(R2)C12(L)21167 (M = Ed,Et; R 5: H or

The mechanism of the

The palladium(1V) complex, fac-CPd(Me) 3(bipy)Il has

An ab initio invest-

The a-methoxyalkyl complex, [ {PdCl-

1 5 5

have been shown to undergo partial H-D exchange with CDC13 solvent. 176 (PEt3l2I (M = Pd, Pt; C10H7 = naphth-1-yl), trans-IMBrtC(Ph)= CMe21(PEt3)21 ( M = Pd,Pt), and t r a n s - C P t B r t C ( C l o H , 5 ) = C H 2 ) ( B E t 3 ) 2 1

(CloH15 = adamant-1-yl) have been prepared and shown to have unusually long Pt-C lsp2 ) bonds The a-allenyl complexes, trans-CPd(R3C=C=CR1R2) (PPh3)2X1 ( X = C1,Brl have been synthesiska! When R3 is a bulky group, the acetylenic isomers, trans-CPd(R1R2- CCrCR3)(PPh3)2Xl (R3 = But,SiMe3; R1 = R2 I HI are obtained.17'


The (0'-ally1 ) arylpalladium complexes of the type [ Pd ( L ) (ql-allyl) 1 (L2 = dppe , Ph2PCH=CHPPh2 ; Ar = C6F5 ,C6HC14) give selective Ql-allyl-Pd bond cleavage on reaction with electrophiles (HC1,Br2,NBS), whereas the corresponding ( q -allyl)aryl palladium complexes undergo selective Pd-Ar bond cleaaage. 17'

anhydride, the (0'-allyl) arylpalladium complexes react to give 1 : 1 adducts arising from [2+31 cycloaddition. 17' The C-bonded heterocycle - containing complexes [{PdCl(R) (PPh3)}21 and trans-[PdCl- ( R ) (PPh3I2J are obtained by the oxidative addition of 2-chloro- pyridine, 2,6-dichloropyridine, 2-chloropyrazine, or 2-chloro- benzothiazole, to [Pd(PPh ),I .180 complexes are reported.

( Ar -

3

With maleic

Some reactions of these 188

The reaction of [Pd3(02CMe)61 with PPh3 gives the phenyl- palladium dimer, CPd2(p-02CMe)2(Ph)2(PPh l 2 1 , which has been characterised by X-ray crystallography. Other alkylpalladium

dimers that have been reported include [{PdMe(SMe2)X}2] ( X = C1, 183 Br,I)182 and [Pd2(p-C1)2(Me) 2 2 L 1 ( L = PEt3,PBu3,PMe2Ph).

phenyl or pentachlorophenyl ligands have been reported. Thus, for example, complexes of the type [(C6F5)2Pd(p-C1)2ML21 (M = Ni,Pd; L2 = dppe; M = Pt; L = PEt3) have been prepared by treating - cis- CPd(C6F5) ( PhCN) ,I with [MC12L2 1 .'* Treatment of =-[M(C6F5 1 - (THFI21 ( M = Pd,Pt) with PhCXPh gives e - [ M ( C 6 F 5 ) 2 ( P h C X P h ) 2 j ! i 1 5

The synthesis and some reactions of trans-CPd(C6C15)X(CNMe)21 (X = Cl,Br,I,SCN) ,186 CM(C6X5)z(dppa)21 and [M(C6X5)2(dppa) 1 (M = Pd,Pt; X = F,C1; dppa = Ph2PNHPPh 2 [XPd(p-dppm)2Pd- (C6Cl5)1 ( X = C1, C6C15) ,188 a n d [ X P t ( p - d p p m ) 2 P d ( C , C 1 5 ) l (X = C1, Br,C6F5)189 have been reported.

tituted :- (benzylidene) amines ,1901191 substituted phenanthroline or bipyridyl groups ,lg2 'lg3 methylbenzalazines ,lg4 # I g 5 and 2-t- - butylbenzothiazole .lg6 The cyclometallated complexes G - E g I o - '

A number of new palladium complexes containing pentafluoro-

Among the ligands involved in cyclopalladatedcomplexes are subs-

* - Ph2PC6H4NC(0)~6H41 to-Ph2PC6H4NHC(0)Ph} 1 (M = Pd,Pt) have been prepared and the platinum derivative has been characterised by

I

- X-ray crystallography .lg7 the dinuclear complexes [((p-Br)M(o-CsH4CH2ER2)}21 ( M = Pd,Pt; E = P,As). A general scheme has been proposed for the reactions of cyclopalladated complexes with alkynes .lg9 alkyne molecule R C X R , inserts into the Pd-C bond of the cyclopalladated complex [PdCl(py)(C6H4CH2C5H4N)1 to give C(PY)C1Pd{C- (R)=C(R)-C6H,CH2C5H4h}J, and a second alkyne insertion takes

A new synthesis has been reported for

One

t

Complexes Containing Metal-Carbon 6- Bonds (Fe, Co, Ni) 28 1

2 00 place to give the spiro-compound (14). The oxidative addition of ICH2P(0)(OR)2 (R = Me,Et) to [M(PPh3)I4]

(M = Pd,Pt) gives the phosphonate ylide complexes, CM(PPh3I2(I)- ICH2P(0) .201 The sulphur ylide complexes CPd(PPh3I2 I(CH2)2S(0)MeElCII and CPd(PPh3) (I) t (CH2)2S(0)Me)l,202 and CPd(p-I) { (CH2)2S(0)Me}12 and related complexes203 have been reported. The metallathiethane-3,3-dioxide complexes [ML2{CH(R)- 7 S(0)2CHRll (M = Pd,Pt; L = PPh3,PMePh2,PMe2Ph; R = COPh, C02Me) have been prepared and characterised (for M = Pt) by &-ray crystallography .204

7

The reactive intermediate [Pt(Cy2PCH2CH2PCy2)l, produced by thermal reductive elimination of neopentane from =-CPt(H) (np)- (Cy2PCH2CH2PCy2)1 (np = neopentyl), reacts with C-H bonds in saturated and unsaturated hydrocarbons to give =-CPt(H) (R) (Cy2- PCH2CH2PCy2)1 (R = SiMe3,cyclopentyl,l,2,2-tetramethylcyclopropyl, Ph,CH2C6H3Me2-3,5, or Mes).

Improved synthetic routes to [PtMe2 (cod) 1 have been reported.'06 Norbornadiene has been displaced from [PtMe2(nbd)l by a range of ligands L to afford e-CPtMe2L21 (L = py,NH$MSO; L2 = bipy, en, h e n ) and by cyanide to give cis-[PtMe2(CN)2)12-. these complexes with Me1 have been investigated .'07

205

Reactions of

Extensive investigations of bis(phenyl)platinum(II) complexes have been reported. Spectroscopic (i.r. and n.m.r.1 studies of complexes of the type cis- and trans-CPt(Ar)2(PBu3)21 (Ar = substituted phenyl group) have provided criteria for the determination of the configurations of these complexes .208t209 and reactivity of C;t{o--C6H4N(0)d}21 has been studied.210 nitro-substituted phenyl complexes, [Pt(L2)(4-XC H4)(4-02NC6H4)I ( X = NMe2,CF3,0Me,Me,N02; L2 = cod or L = PPh3)"l and CPt ( L2 ) I2,4- (02N 1 'C6H3 1 (aryl) I2l2 have been synthesised. Other phenylplatinum complexes that have been synthesised and studied include [Pt(DIOP) (4-XC6H4)21 (X = CF3,SiMe3,0Me) ,'I3 and [Pt(Ar)(4-Me3SiC6H4)(PPh3)21 of increasing acceptor character). 214 yl) (PPh3 1 I2l5 and CPtI ( E ) - Z - e t h o x y n a p h t h - l - y 1 ) 2 (nbd) been prepared: the latter complex has a stationary E-conformation with no rotation about the Pt-C a-bonds. The light induced elimination of biphenyl derivatives from [Pt(Ar)2(L2)I [Ar = substituted phenyl; L2 = d p p e , g - P h 2 P C H C H P P h 2 , o - - ( P P h ) C H 1 proceeds by a non-radical concerted reaction mechanism.

The oxidative addition of vinyl triflates to C P ~ ( P P ~ ~ ) ~ I gives

The synthesis The

(Ar = phenyl ring with substituents Cis- [Pt (7-methylnaphth-l-

have

-

2172 '


ii MC3

I I Et3P-Ni-Si-SiMe,

I I kt, Mes

( 1 3 )

( 1 5 )

cp co \ /

Pd

OMe

( 1 6 1

Me 0

- CI

( 1 7 ) (18)

Complexes Containing Metal-Carbon b- Bonds (Fe, Co, Ni) 283

the platinum(I1) complexes, CPt(PPh3)$R)1COTfl (R = various u- vinyl ligands ) . 218 The alkynylplatinum complexes cis- C Pt ( CXPh) 2-

L2] 219 their isomerisation to the trans isomers has been studied. The alkynyl complexes trans-CPtC1(CXR)(PEt3)21, trans-CPtC1- (CSCR)2(PEt3)21, and t r a n s - [ P t ( C E C R ) ( C 3 2 R ' ) ( P E t 3 ) 2 1 (R = H,Me,Ph; R' = H) are produced by treatment of trans-CPtC12(PEt3)21 (or the mono-alkynylplatinum complex) with the appropriate alkynylstann- ane.

(L = PPh3,PMePh2) have been prepared by various routes, and

220

The reaction of CPt(q'-Cp) (Ph) (cod) j with PPh3 leads to coupling of the cyclopentadiene and cyclooctadiene groups to give complex (15). 221 nucleobase complex [(NH3)4Pt2(C5H5N202)31[(SiF6)(N03).7H201, in which one of the 1-methyluracil ligands is a-bonded to platinum at the deprotonated C(5) position, has been reported.222 This provides the first example of a platinum-nucleobase complex containing a Pt-C a-bond.

The preparation and structure of the platinum-

An investigation of the reactivity towards oxidative addition of Me1 of mononuclear and binuclear dimethylplatinum complexes containing various bis(diimine) ligands has shown that the binuclear complexes always react more slowly than the mononuclear complexes. 2 2 3 complexes [PtI(Me)2(CHXCH2R) (phenll CX = CN,CHO,C(O)Me; R = Pri or But] are produced by a free radical chain reaction when [Pt- (MeI2(phen)1 reacts with PriI or ButI in the presence of the alkenes CH2=CHX. 224 The preparation and reactions with alkenes and alkynes of the complexes CPt2(p-C1)2(Me)2(C2H4)21 and CPt2- (p-C1)2(Me)2(C0)21 are reported, together with a number of novel dialkylsulphide complexes including the platinum(1V) carbonyl complex fac-CPtI(Me)3(SMe2)(CO)l. 225 lexes e - C P t ( 2 - p h e n y l p y r i d i n e ) 2 ] and cis-[Pt{2-(2'-thienyl)- pyridineI2l undergo stereoselective oxidative addition of alkyl halides to give platinum(1V) complexes with the halide and u- alkyl ligands mutually cis. 226 Thermal oxidative addition reactions with these complexes yield mixtures of several isomers which rearrange to one of the possible cis isomers.

Me)]+X- (2 = 3 : E = E' = s; g = 2 : E = Se or S, E' = o,s,s~, or -SS-; X = I,BPh4, or BF4) and CPtMe3(H2NCH2CH2)2EJ+BF4- (E = 0 or -SS-) has been reported.227 The preparation and n.m.r. studies of platinum(1~) complexes of the types C(PtXMe3)2(ECH2CMe2CH2E)]

The functionally substituted organoplatinum ( IV 1

The cyclometallated comp-

226

The preparation of the complexes [PtMe3{MeE(CH ) E'(CH E- 2 1 2 2

-


(E = S or Se; X = C1,Br,I)228 and [(PtXMe3)2{HC(SMe)3)1 (X = C1 or Br 229 have been published.

A full report has been published of the reactions of CPt(PPh3)41 and [Pt(C2H4)(PPh3)2] with CH2C11 to give *-[Pt(CH PPh3)C1- (PPh3)23CII and [Pt(CH2C1)I(PPh3)21, respectively. 236 A number of

chloromethyl complexes of the type [PtC1(CH2C1) (L)] (L = chelating olefinic ligand) have been prepared by treatment of the dichloro- platinum complex with diazomethane. 231 uced oxidative addition of CH2C12 or CHC13 to the luminescent ortho-metallated complexes [Pt(Thpy)2] and [Pt(Ph~y)~l [Thpy = C- deprotonated 2-(2-thienyl)pyridene; Phpy = C-deprotonated 2-phenyL pyridine] gives the luminescent platinum(1V) derivatives CPt- (Thpy)2(CH2C1)C11 and [Pt(Thpy) Phpy derivatives, respectively. 332 The synthesis of [ClPt- (p-dppm),Pt(c F 1 3 and some of its chloro-substituted derivatives h a s been described.233 structures of CNBu4I2- CPt(C6C15)41, C N B U ~ I C P ~ ( C ~ C ~ ~ ) ~ I , and C N B U ~ I [ P ~ ( C ~ C ~ ~ ) ~ N O ~ have been reported. 234 of a mononuclear platinum(II1) complex. The carbonylation of - cis-[Pt(C6X5)2(OC4H8)21 (X = F,C1) gives cis-[Pt(C6X5)2(C0)21, while carbonylation of C N B ~ ~ l C t r a n s - P t ( C ~ F ~ ) ~ C l ( C 0 ) 1 in the presence of AgC104 gives trans-[Pt(C F ) (CO)2J.235 of these complexes have been investigated.

The mechanism of the protonolysis of the neopentyl complex [PtX(CH2CMe3)(PEt3)21 ( X = C1,Br) by HX has been studied.236 mechanism of the thermal decomposition of CPt(CH CH CH CH )(L),I ( L = PCy3) to give 1-butene and [PtL21 as major products, of tran~-[Pt(Np)Cl(L)~I( L = PCy3; Np = neopentyl) to give trans-CPt(H)C1(L)21 and l , l - d i m e t h y l c y ~ l o p r o p a n e , ~ ~ ~ have been investigated. The asymmetric complex cis-[Pt(PEt3)2(CH2CMe2Ph)- (2-C6H4CMe3)1 has been synthesised and structurally characterised, and shown to undergo aromatic rather than aliphatic 6-C-H transfer to give t-butylbenzene and the platinaindan [(Et3P)2Pt(2-C H - 7 CMe2CH2)I. - 239 A study of thermal decomposition of the methoxo and ethyl complexes [Pt(dppe)(OMe)21, CPt(dppe1 (EtI2l, and CPt(dppe)(Et)(OMe)l has led to the suggestion that B-elimination from the ethyl ligand is energetically easier than the comparable process from the methoxo ligand.

The platinacyclic complexes, [Cl, ( L 1 26tCH2CR: (CHR20R3 )AH2 1 (R1 = H,Me,Ph; R2 = H,Me; R3 = methanesulphonyl or 4-nitrobenzoyk L = py or L2 = bipy) undergo ring expansion on solvolysis in

The photochemically ind-

(CHC12)C11 and the corresponding

6 5 The syntheses and

The latter complex represents the first example

Some reactions 235

The - ? 3 7 and

1

6 4

240


aqueous acetone to give the platinacyclopentanol products, [C12 (L)2:tCH2R2CR1(OH)CH2kHzl .241 The scope and mechanism of this ring expansion reaction are discussed .241 diene complex, L(PPh3)2PtC(Ph)=C(Ph)C(Ph)=CH:H21 is formed by a ring expansion reaction between 1,2,3-triphenyl-3-vinylcycloprop-

1-ene and CPt(PPh3)2(C2H4) The organoboration of CPt(dppe)- (C:CH)2] o r [Pt(depe)(CXH)21 with BR3 (R = Me,Et,Pri) gives the platinacyclopentadiene complexes, C (L2)$t tCH=C(R)C(BR2)=tH}l .243

7 A new route to the platinasilacyclobutane complex, [(PPhMe2l2Pt- CH(SiMe3)Si(Me)2kH2], by treatment of [PtCl(SiMe3)2(Me)(PPhMe2)21

with tBuLi has been reported. 244

The platinacyclohexa- t

3 Carbene and Carbyne Complexes of the Group VIII Metals

3.1 The Iron Triad,- The iron-methylene and -hydroxymethylene Complexes C(C5Me5)(CO)2FeLl (L = CH2 or CHOH) have been prepared by treatment of [ (C5Me5) (CO)2Fe(CHzOH) 1 with CF3S03SiMe3 .245 Hydride abstraction with Ph3C+PFi from the methoxymethyl complex [(C5Me5) (C0)zFe(CH20Me)l affords the methoxycarbene complex [(CsMes) (CO)2Fe{=C(H)OMe)l[PF61, which undergoes an addition reaction with PPh3 to give [ (C5Me5) (C0)2FetC(H) (OMe)PPh3}l[PF61!46 Carbonylation of the carbene complex [(Cp) (C0)2Fe(=CH2)l, followed by methanolysis leads to the formation of [(Cp) (CO) Fe(CH2C02Me) 1 , a precursor for the synthesis of a malonic ester. 24' The carbene complex (16) is obtained on photolysis of [ (Cp) (C0)2Fe{e(OMe)CH - CH2CH2 1 1 , 248 and photolysis of the 1-methoxybenzocyclobutenyliron I 2

complex [(Cp) (C0)2Fetl-(MeO)CCH2C H411 giues a mixture of the carbene complexes (17) and (18). 299 The acylcarbene complexes [(CO),Fet=C(OR)(COCMe3))1 (R = Et, SiMe3, MeCO) have been prepared. 250 The stereoselective hydride reduction of C (Cp) (C0)- ( P P h 3 ) F e ( = C w M e 2 ) I+ to (RR,SS)-[ (Cp) (CO) (PPh3)Fe{t(H)OCH2- I CH2CMe2}1, and its subsequent epimerisation to the thermodynamically more stable (RS,SR)-diastereoisomer, has been rationalised by a conformational analysis .251

The aminocarbene complexes, c (CO) 4Fe ( =C (R 1 NMeZ 1 1 (R = Ph ,Bun, Me) give rise to the formation of 5-(dimethylamino)furans on reaction with alkynes. Under high CO pressure, these complexes give 6- (dimethy1amino)pyrones .252 The crystal structure of the trigonal bipyramidal electron-rich carbeneiron complex [(COl3- (PEt3)Fe{&N(Me) (CH2)2iMe}l has been determined.253 The electron-


L 0


1 rich dithiolylidene complex, [(L)2(C0)2Fe{=:SC(C02Me)C(C02Me)S}j (L = PMe2Ph) undergoes protonation at the carbene carbon centre, but the reaction proceeds a metal to carbene 1,2-hydrogen shift.254 The dithiocarbene complex [ (Cp) (CO) (MeCN)Fe=C(SMe)21+ reacts with [Fe(C0)3(NO) 1- to afford the complex (19) .255 reactions have been carried out using ruthenium and cobalt complexes.

Similar

255

A new, high yield route to [Fe2(p-CH2) (CO)8] involving addition of [Fe(CO)5] to a CH Br2;H20/NaOH;(Bu4N)2S04 phase transfer system has been moiety in CFe (p-CH2)(C0)81, in cryogenic matrices, has been identified. 255 Ketene formation by CO insertion into the p-methylene ligand of the complex [Fe2(p-CH2) (CO) ation of the new complexes [(CO),F'eCH2CH2C(0)EH21 and C(CO)4F~C(0)- CH=C(OCOMe):H21 .258 An n.m.r. study of the cis/trane isomerisation of the p-methylene complex C {FetCp) ( C X l ) y p-CO) ( p-CH2 1 1 has led to a proposed mechanism for the ismerisation involving the breaking of the Fe-Fe bond in the rate determining step.259 the p-methylidyne complex [{Fe(Cp) (CO))2(p-CO) (p-CH)l+ with a variety of alkenes to give either p-alkylidyne or p-alkenyl complexes, and studies to determine the factors influencing the reaction products, have been reported .260-264 (C0))2(p-CCH2CH2)1 undergoes thermal or photochemical rearrangement to the p-allene complex C(Fe(Cp) (CO) I2(p-CH2=C=CH2) 1 ,265 and protonation to give the p-propylidyne complex C{Fe(Cpl(C0))2(p- CCH2CH3 1 3' which undergoes deprotonation to give the p-methylvinyl- idene complex i{Fe(Cp)(CO))2(p-C=CHCH3)1. 266

n complex C{Fe(Cp)(CO))2(p-CO)(p-CCH2CHC02Et)l also undergoes acid- catalysed ring-opening to afford the p-alkenylidene complex CtFe(Cp) (CO)~2(p-CO)tp-C=C(H)CH2C02Et)3. 267 The photolysis of [{Fe(Cp)(CO)12(p-C=CH2)l in the presence of ethyl diazoacetate glues the allene complex CtFe(Cp)(CO)12(p-CH2=C=CHC02Et)l. 267 The alkyne HCECCN reacts with the ethenylidene complex c{Fe(Cp)(CO)l - (~-CO)(I.I-C=CH~)I to give [CF~(CP)(CO))~(~-CO)(~-C=CHCH=C(CN)H)~. 2g8

The p-vinylidenedi-iron complex (20) has been obtained either by treating CFe( n4-C6H6 1 ( tmps 1 J L tmps = MeSi (CH2PMe2 1 1 with ethylene, or by the sodium amalgam reduction of [FeC12(tmps)l in the presence of ethylene .269 The stable bimetallic carbene complexes [C12HgFe(CO)2(L)2{=CsC-

(C02Me)C(C02Me)i}l beenobtained by treatment of the appropriate iron-carbene C o m p l e x

The vibrational spectrum of the Fe2CH2

1 leads to the forrn-

The reactions of

The p-cyclopropylidene complex c {Fe (Cp) - rn

The cyclopropylidene

I

(L = PMe2Ph,PMe3,P(OMe)3,PPh3) have been


with HgC12. 270 ment of the electrophilicity of the carbene carbon. 270 (n-ally1zirconoxy)iron complexes (21) ( L = CO or PPh3) are produced by a carbon-carbon coupling reaction between (butadiene)zirconocene and CFe(C0)5) or [Fe(C0)4(PPh3)1, respectively.271 mixed-metal p-methylene complexes, such as the iron-iridium complex [(C6Me6)(CO)Fe(p-CH2)Ir(C5Me5)(CO)l, have been synthesised using [Fe(r16-C6Me6)21 as a source of the LFe(C6Me6) 1 fragment. 272 Ot.her heterobimetallic complexes of interest are [FeCo(CO) (p-CH=CPhHfj:

The reactivity of these complexes shows an enhance- The

A number of

[ (CO) 3Fe ( p-CO) ( p-C=CHPh Rh (PPr$Cp 3 and [ (CO) 3Fe {p-C ( 0 ) C (Ph =CH 1- Rh(PPr$Cp) I ,274 and the iron-molybdenum complex CFeMo(p-CC6H4Me-4)- (co)~(c~) I . ~ ~ ~ The electronic structure of the carbene [RuCH2]+ has been

investigated by ab initio methods276 and contrasted with that of [CrCH2]+ which has allowed a separation of a-donor bond strengths from n-donor bond strengths and a prediction of the stabilities of CLnM(CXY)l complexes for the whole transition series. 277 Hydride abstraction from C Ru (Cp 1 (dppe 1 ( Me 1 1 gives the methylene complex [ (Cp) (dppe)Ru=CH21+, which has been studied using n.m.r. spectroscopy . 7 8 The methoxy- or hydroxy-carbene complexes trans- [M(r€H- (oR)Mco)(P-P)~J~+ C M = ~ u , o s ; R = Me or H; P-P = dppe or 1,2-(Ph2- P)2C6H4J are formed on treatment of the formyl complexes trans- CM(CH0) (CO) (P-P)21+ with electrophiles (CF3S02Me or MeS02H) .279 The carbene complexes are attacked at the carbene ligand by hydride donors to give trans-[M(CH20R) (CO) (P-P)2]+. The implications of these reactions on the mechanism of homogeneous CO hydrogenation are discussed. 279 The alkoxyalkylcarbene complexes [Ru{ =C (OMe) - CH2RjC1(PRt3) (C6Me6)l+ (R = Ph,But,H) are formed, via a vinylidene- ruthenium intermediate, on reaction of [RuCl2(PRI3) (C6Me6) 1 with RCXH . 280 If HOCH2CH2CXH is used in this reaction, intramolecular cyclisation occurs to give [ R U ( = C C H ~ C H ~ C H ~ O ) C ~ ( P R ' ~ ) (C6Me6) l[PF:y!

PCHRCHR'PPh2; R,R' = H or Me) react with methyl Grignard reagent to give the corresponding phenylacetylide complexes [(Cp) (P-PIRu- (CECPh) 3 .281

I

The carbene Complexes [(Cp)(P-P)Ru{C(OMe)CH2Ph11[PF61 (P-P = Ph2-

The p-ketene complex C R U ~ ( C O ) ~ ( ~ + C O ) ( ~ - C ( O ) C H ~ } ( C ~ M ~ ~ ) ~ ~ is produced by oxidation of the p-vinylidene complex [RU~(CO)~(~-CO)- (p-CCH2) (C Me 1 1 .282 Subsequent decarbonylation of the p-ketene complex occurs readily to give [Ru~(CO)~(~-CO)(~-CH~)O Me5I2]

which is carbonylated to C R U ~ ( C O ) , ( ~ - C ( O ) C H ~ } ( C ~ M ~ ~ ) ~ ] . 282 The

5 5 2

Complexes Containing Metal-Carbon @-Bonds (Fe, Co. Ni) 289

zirconoxycarbene rutheniym complexes ( 2 2 ) and (23) have been prepared. 283 The crystal structure of the difluorocarbene complex COs(=CF2)-

Cl(N0) (PPh3I2l and its conversion to the trifluoromethyl complex [Os(CF3)C1X(NO)(PPh 1 1 by reaction with halogens X2 ( X = C1,I) have been reported. ”‘ The dichlorocarbene complex [ O s ( =CC12 ) C12- (CO)(PPh3)21 reacts with LiR ( R = a-tolyl) to give the carbyne complex [Os(ECR)C1(CO)(PPh3)21 whose crystal structure has been determined. 285 The carbyne complex reacts with electrophiles such as HC1 to give [Os(=CHR)C1~(CO)(PPh3)21 or C12 to give [Os(=CHCl)- C12(CO)(PPh3)21, and with metal halides to give [O;{=C(hX)R)Cl- (CO)(PPh3)21 (MX = CUI,AgCl,AuCl). 285 structure (for R = But) of the vinylidene complexes [Os(=C=CHR)- (CO) (PPh3) (C5Me5) ICBF41 (R F But,Ph) have been reported together with the alkyl complexes [-Os(C Me )(CO)(L)(R)I (L = CO, R = Me,Bu, Ph; L = PMe3, R = Me; L = C2HQ, R = Me). 286 The vinylidene osmium complex [ (C6H6) (PPr!j)Os(=C=CHPh) 1 reacts with benzoylazide to form the metalla heterocycle c ( c ~ H ~ ) (PPr;)$s{C(=CPhH)N=C(Ph)611; a similar reaction has been carried out on the rhodium complex [ (Cp) (PPri)Rh(=C=CHR) 1 .287

The preparation and

5 5

The p-methylene cluster [ O S ~ ( C O ) ~ ~ ( ~ - C H ~ ) ~ reacts with SnC12 to give the planar cluster COs3SnC12 (CO) 11 ( p-CH2 1 , 288 and with [Pt(C2H4)(PPh3) 1 to give the tetranuclear cluster [Os3Pt(p-CH2)- (CO)11(PPh3)21. Treatment of [Os3 (CO) 11 (p-CH2 1 1 with ethylene sulphide gives [ O S ~ ( C O ) ~ ~ ( ~ - S C H ~ ) ~ and [Os3(CO)lo(p3-SCH2)1. 2 90

The carbene cluster complex [Os3(CO) goes photodecarbonylation to afford [Os3(CO)8(p-C=NMe2)(p-SPh)- (p-H)] by an =-C-H bond activation in the carbene ligand.291 Pyrolysis of the trimethylamine complex Cos3(CO)8(NMe3)(p3-SC6H4)- (p-H121 yields the first examples o f hexanuclear clusters that

tC(H)NMe2}(~-SPh)(~-H)1 under- 9

contain carbene ligands, three isomers of [OS,(CO)~~{C(H)NM~~)- (IJ~-S)(~~-S)(LI-H)~I. 292

3 . 2 The Cobalt Triad.- It has been shown that reactions of meth- oxyalkylidene cobalt complexes, [ C O ( C O ) ~ ( S ~ P ~ ~ ) C = C ( R ) O M ~ } I (R = Ph, Bun) with alkynes occur with exclusive formation of 2-alkoxy- furans. 293 The cationic carbenoid cobalt complexes, CCo(Cp)- (CH2Cl) (PMe3) (CNAr 11’ are formed on treatment of CCo(Cp) (PMe 1 (CO)] with aryl isocyanides, CNAr (Ar = Ph,C6H4Me-4) and CH2C11. 2 9a

Addition of KOH to these carbenoid complexes gives the cobaltadi- 29

hydroquinoline derivatives [ (Cp) (PMe3)Cb{CH2-2-C6H3(4-R)N=?(OMe) 11.


+-y-hMT& "T H,Ph

Me Me

Ph

Ph,

/ P ' CL

Ph2

/Pt,C,/Pd-c\p/ - "Pt/ \ c , / \Pd=C\ \

29 1 Complexes Containing MetalLCarbon o-Bonds (Fe, Co, Ni)

The diaminocarbene complex cCo(Cp) (CO){C(NHMe) (NHPh)l(PMe3)l loses CO at 60°C in acetone to give C(Cp)(PMe3)Cb{(o-C6H4)N(H)~(NHMe)}l

iPFs 1.

type [C~~(p-R)(p-R')(CO)~(p-dppm)l (R = CH2,CHMe,CHC02Et; R' = CO, CH2,CHMe,CHC0 Et,S02) to give RCH=C=O (R =H,Me,C02Et) has been investigated. 296 When Na[Co(CO) 4] is treated with dif luoromalonyl dichloride, ClOC-CF2-COC1, at room temperature, the u-difluoro- methylene complex [(CO)3Co(p-CO)(p-CF2)Co(CO)31 is formed in high yield. 297 introduction of CF2 bridges.

formed on treating CRh(Cp)(C0)21 with bis(l,3-dimethylimidazolindin -2-ylidene). 298 addition of an alkyne to a M=C double bond has been reported;"' the experimental reaction involves the reaction of CF3CXCF3 to [Rh ( triphos )C1( q2-CX2 1 1 (X = S , Se 1 to give the metallacyclobutene complex, ( t r i p h o s ) C 1 1 h C ( C F 3 ) = q C X C ( C F 3 )=C(CF3)Xl .'" The thermal decomposition reactions of CI(C5Me5)Rh)2(p-CH2)2-

(Me)2] to give methane, propylene, ethylene, and some ethane have been investigated. 300 decomposition products arise, and the relationships of the mechanisms proposed to the mechanism of the Fischer-Tropsch reaction on metal surfaces have been discussed.300 E (C5Me5)2Rh2(p-CH2)2C121 with RCECMgC1 (R = Ph or But) gives trans-[(C Me 1 Rh (p-CH2)2(CECR)21, but with BzMgC1, attack at one - 5 5 2 2 C5Me5 ring as well as at one Rh centre occurs to give the crystallographically characterised complex (24). 301 Treatment of CCp2Ti- Rh(cod)(p-CH2)(p-C1)l with MeLi gives the p-methyl complex CCp2Ti- (p-CH2)(p-CH3)Rh(cod)l in which the methyl group forms a three- centre two-electron agosti-c bond with the Ti atom. Protonation of the alkenylidene iridium complex c ( PPri 1 2C11r-

( =C=CHR 1 I occurs at the metal to give [ ( PPri ) 2C1 ( H) Ir ( =C=CHR 1 I+ which rapidly rearranges in solution at room temperature to the carbyne complex C ( PPr: 1 2ClIr ( ZCCH2R 1 1. 303

295

The coupling of v-alkylidene groups with CO in complexes of the

This method is of potential general utility for the 297 -

The rhodium carbene complex, CRh(Cp) (CO)tCN(Me)CH2CH2N(Me) 1 1 is

An experimental and theoretical study of the

Labelling studies have shown how these

Treatment of trans-

302

3 . 3 The Nickel Triad.- The p-vinylidene complex [Pd2C12(p-dppm,)2- (p-C=CH, 1 1 has been prepared. 304 The preparation and crystal

'A

structure of the p-alkylidene complex (25) has been reported.305 The infinite chain carbene complex [Pb(p-C1)2Pt{E(PPh2)2}l~ (24J6

is obtained on treatment of [PdC12(PhCN)21 with CPt(Ph2PCHPPh2)21. -


The vinylidene complex [Pt3(H) (p3-q2-C=CH2) (p-dppmI33+ has been isolated from the reaction of acetylene with [Pt3(p3-H) (p-dppm)31+, and provides a model for the chemistry of acetylene on the Pt(II1) surf ace. 30 7

A number of heteronuclear metal complexes containing p-carbene or p-carbyne ligands have been reported. Such complexes include [ (Cp) (CO)2W{p-q1,~3-C(C H4Me-4) (HI )Pt(PEt3)21[BF41 ,308 [Pt3W2(p3- CR12(CO) ( c ~ d ) ~ ( C p ) ~ I ,389 [Pt2W3(p-CR)2(p3-CR) (CO)6(Cp)31 (R = C6- H4Me-4), jog [ Pt3W4 ( p-CR) ( p3-CR) (CO) (Cp) 4 1 , 310 and [Pt4W4 (p-CR) -

310 (p3-CR)3(CO)8(Cp)41.

Bibliography 2 G. Bellachioma and G. Cardaci, Gazz. Chim. Ital., 1986, 116, 475. Alkyl and q -

acyl derivatives of iron(I1) complexes: a new preparative method. S.I. Vdovenko, 1.1. Guerus, and Y.L. Yagupolskii, J. Organomet. Chem., 1986, 3 195. carbonyls . G. Consiglio, F. Morandini, G.F. Ciani, and A. Sironi, OrgaImIIetdliCS, 1986, 5, 1976. Stereochemical studies on the interconversion of alkylidene, carbene, and alkyl ligands in chiral ruthenium complexes. E.C. Constable and J.M. Holmes, J. Organmet. Chem., 1986, 301, 203. metallated analogue of [R~(bipy)~I. H. Werner, H. Kletzin, A. Hzhn, W. Paul, W. Knaup, M.L. Ziegler, and 0. Serhadli J. Organomet. Chem., 1986, 306, 227. (Ethylene)(hydrido)metal complexes from lM(=CH2)MeJ (M = Ru,Os,Ir) ~pounds .

Intramolecular &-trans isomerisation of bis(perfluoroalky1)iron tetra-

A cyclo-

L.J. Sanderson ard M.C. Baird, J. Organomet. Chem., 1986, 307, C1. addition reactions of COs(C5Meg~(CO)(PMe2Ph)(Me)r.

Oxidative

S. Fukuzumi, K. Ishikawa, and T. Tanaka, Chem. Lett., 1986, 1. Oxidation of - cis-dialkylcobalt(II1) complexes by oxygen. acid. U. Maer, T. Jenny, and A. von Zelewsky, Helv. Chim. Acta, 1986, 69, 1085. Cyclometallated rhodium(II1) complexes with diimine ligands. G. Favero, S. Issa, A. Turco, and U. Vettori, J. Organomet. Chem., 1986, 315, 237.

Activation of oxygen by perchloric

Reactions of dioxygen with benzylnickel complexes. A.D. Ryabov, A.V. Usatov, V.N. Kalinin, and L.I. Zakharkin, Bull. Acad. Sci. USSR, Chem. Sci., 1986, 35, 1105. ligands .

Exchange of cyclopalladated phosphorus donor

R.C. Mehrotra and S.K. Agarwal, Syn. React. Inorg. Met-Org. Chem., 1986, 16, 213. palladium(I1J and platinum(I1). R. Sustmann, J. Lau, and M. Zipp, Recueil, 1986, 105, 356. complexes. S.I. Murahashi, Y. Kitani, T. Uno, T. Hosokawa, K. Miki. T. Yonezawa. arad N.

Synthesis and characterisation of C-bonded (1,5-cod) alkoxo derivatiGs of

Di-palkylpalladium Thermolysis and r e a c t i m h olef ins-

Kasai , Organometallics , 1986, 2, 356. palladium complexes.

a-diazomethyl and bis (a-diazomethyl)


1 2 3

4

5 6 7

8

9 10 11 12 13

14 1 5 16 17 18 19 20

21

22 23

24 25

26 27 28 29

30 31

32

33 34 35

36

37 38 39

40

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G . M . Sheldr ick H . A . Brune, B. 129. H.A. Brune, B. H.A. Brune, R. 311, 27. H.A. Brune, R . 429. H . A . Brune. W.

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228

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264 C.P. Casey, M.W. Meszaros, R.E. Colborn, D.M. Roddick, W.H. Miles, and M.A. Gohdes, Organometal l ics , 1986, 5, 1879.

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294 K W e r n e r , L. Hofmann, M.L. Ziegler, and T. Zahn, Organdmetal l ics , 1986, 5 . 510.

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Complexes Containing Metal-Carbon a-Bonds (Fe. Co, Ni) 30 1

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Chem. Comun., 1986, 431.

13 Metal-Hydrocarbon n-Complexes, other than n-Cyclopentadienyl and n-Arene Complexes

BY M. W. WHITLEY

A Reviews

Reviews have been publ ished on f l u x i o n a l i t y i n polyene and polyenyl metal 2 complexes’ and on t h e chemist ry o f cyclopentadienylmolybdenum a1 kyne complexes.

I n addi t ion, reviews on t h e organic chemist ry o f dicarbonylcyclopentadienyl i r o n

compounds3 and t h e reac t i ons o f saturated hydrocarbon-bridged d inuc l ear

c o m p ~ e x e s , ~ con ta in ma te r ia l o f i n t e r e s t .

-

- B 1 C r y Mo and W

[ C r (CO

temperature nmr spect ra o f [M(C0I2(q-maleic anhydride) (q-hexaethyl benzene)]

( M = C r , Mo) have been inves t i ga ted and the s t r u c t u r e f o r M=Mo determined

c r y s t a l l o g r a p h i c a l l y . 6

achieved by r e a c t i o n o f ethene w i t h cyc lometa l la ted

a l t e r n a t i v e l y w i t h t h e formaldehyde complex8 [W(H)2(PMe3)4(n2-CH20)l. The

0x0-a1 kene complexes [WCl2(O) (PMePh2)2(n-CH2=CHR)1 (R=H,Me, CH=CH2) have been

prepared and cha rac te r i sed c rys ta l l og raph ica l l y f o r R=H. K i n e t i c s tud ies have

been made on r i n g c losu re v i a a1 kene coo rd ina t i on f o l 1 owing p i p e r i d i ne

d i ssoc ia t i on ’ f rom cis- {W-PPh2(CH2) 3CH=CH2) (CO ),(pi p e r i d i ne 1 I.

i n t h e syntheses o f t r i s a l l y l complexes [MoXL(rl - C 3 H 5 l 3 1 [X=C1 o r a l k y l ; L=PMe3,

o r P(OMel31, [Mo L2(~3-C3H5)31Z [z=+l, L2=en o r dmpe; z=O, L 2 =acacl,

[ M O L ~ ( ~ ~ - C ~ H ~ ) ~ I [L=PMe3, o r P(0Me) I and [ M O R ( ~ I ~ - C ~ H ~ ) ~ I (R=al k y l w i t h an

agost ic B-C-H-+Mo i n t e r a c t i o n ) . l1 y 1 23 The so l vent dependent r e a c t i o n o f

Ph4P[MoC1 ( C 0 ) 3 ( b i p y ) l w i t h C l C H C=CCH2C1 g ives e i t h e r (1

adduc t1

Ph4P[MoCl ( C 0 ) 3 ( b i p y ) l i s be l ieved14 t o g i ve (2). The syntheses o f

[MoCl ( CO ) ( NCMe ) 2{n3- 2- ( CH2C1 1 C3H4 11 and t h i osemi c arbazone compl exes

[MOX(CO),(RR’CNNHCSNH~) (n-C3H5)1 (X=halide; R=H o r Me; R’=al k y l o r phenyl 1 are

reported,15y16 and t h e reac t i ons o f [ M 0 B r ( C 0 ) ~ L ~ ( q ~ - a l l y l 11 (L2=N- o r P-donor)

A1 l y l Compl exes and Complexes Derived from Monoal kenes

Photo lys is o f Cr(COI6 i n ethene-doped l i q u i d xenon y i e l d s 5 -

(q-ethene 11 toge the r w i t h cis- and t rans - [Cr(CO ),(q-ethene) 21. Var iab le

Synthesis o f trans-[W(PMe 1 ( r ~ - e t h e n e ) ~ l has been 374 n

[{W-PCH2Me21(H) (PMe3l41 o r

9

Dimeric [ {MO(T I~ -C~H~)~ ( ! J -C~ has been repo r ted as a s t a r t i n g ma te r ia l 3

o r i t s methanol

C ( Me ( OMe 1 I ; w i t h C 1 CH2C X H , 2-1 [ MoC 1 ( CO ( b i py { q3-CH2 -C ( C02Me


302

MetaCHydrocarbon n-Complexes 303

w i t h HgX2 (X=Cl, CN o r SCN) have been i n ~ e s t i g a t e d . ' ~ A c r y s t a l s t r u c t u r e 3 determinat ion o f [Mo(NCS) (CO)2(phen)(n -1-syn-Ph-C H 11 revea ls asymmetric

molybdenum-ally1 bonding; t h e synthes is o f [ M O ( C O ) ~ ( ~ -1-syn-Ph-C3H4)Cpl i s a repor ted.

I C ~ ( ~ I ~ - C ~ H ~ ) ~ C P I has been prepared and cha rac te r i sed c r y s t a l l og raph ica l subsequent reac t i ons l ead t o reduc t i ve coupl ing o r displacement o f t h e a l l y l 1igands.l' The s t e r e o s e l e c t i v i t y o f carbanion a d d i t i o n t o t h e a l l y l l i g a n d i n

[Mo(CO)(NO)(n - a l l y 1 ) ( r i n g ) ] + (r ing=Cp o r CH3COCp) depends p r i m a r i l y upon t h e exo/endo conformat ional preference o f t h e a l l y l l igand.20y21 Regiocontrol l e d

carbon-carbon bond fo rma t ion i s observed i n e l e c t r o p h i l i c a d d i t i o n t o t h e n i t r i l e s t a b i l i s e d carbanions der ived f rom treatment o f (3) o r [ M O ( C ~ ) ~ ( ~ ~ - C H ~ - C H = C ( C H ~ ) ( C H ~ C N ) ) C ~ I w i t h BunLi .2'y23 Bromine ox ida t i on o f

[Mo (CO 1 ( n3- 2-R-C3H4 1 Cp I ( R=Br ,C1 ,Me 1 g i ves Mo ( I V 1 compl exes I M O ( B ~ ) ~ ( C O ) (q3-2-R-C H )Cpl; reduc t i on o f t h e m e t h a l l y l d e r i v a t i v e i n t h e

presence o f PPh3 a f f ~ ? d ; ~ ~ [Mo(CO) (PPh3) (n3-2-Me-C3H4)Cpl. The exo and endo isomers o f [Mo(X)(Y)(q - a l l y 1 )Cpl (X=Y=CO; X=CO, Y=NO+; X = I - Y=NOt) may be

d i s t i ngu ished by 95M0 nmr spectroscopy.

43 18

3

3

Reaction o f tri scarboxyl a te

so

a l ky l i dynes [MXBut (02CR)31 (M=Mo, W; R=a lky l ) w i t h alkynes R 'CXR ' (R'=Me, E t

o r Ph) y i e l d s cyc lopropenyl complexes26 IM(n3-C3ButRt2) (O2CRl31.

2 Fe, Ru and 0s

[Fe(C0)2_x(N0)2(n-1-butene) I (g= l o r 2); t h e p h o t o l y t i c synthes is o f [Fe(depeI2 (n-ethene) 1 f rom c i s - [Fe(H 1 2(depe 1 21 and etheneZ8 proceeds via t h e i ntermedi acy o f cis- [Fe(H (TCH=CH2) (depel21. Crysta l 1 ographica l l y

cha rac te r i sed [Fe(q6-toluene) (n-ethenel21 undergoes s y n t h e t i c a l l y usefu l ethene

displacement reactions." A1 kene complexes [Fe(C0),(n-CH2=CHR)(Me5Cp)l (R=H,Ph)

are formed when i n s e r t i o n o f t h e carbene fragment i n IFe=CH(OMe)(CO)2(Me,Cp)l i n t o an S i - H bond i s c a r r i e d ou t i n t h e presence o f t h e alkene.30

27 -

Photo lys is o f IFe(C0)2(N0)21 i n 1 -butene doped l i q u i d xenon a f f o r d s

I5

Var iab le

5-subst i t u t e d ~7-oxabicyc l0 [2.2.1 lhept-2-ene 31P and 'H nmr i n v e s t i g a t i o n s have been c a r r

o f alkenes, CH2=CHR (R=H,Me,Ph,acyl), i n [Ru(PPh2CH(Me )CH (R ' 1 PPh2) (s-CH2=CHR)Cpl+ (R' complexes [MH (n-ethene) ( PR,) (n-hmb) 1' (M=Ru,

temperature c i r c u l a r d ichro ism measurements have been made on a se r ies o f t e t raca rbony l i r o n complexes3' and

ed ou t on t h e enant io face s e l e c t i o n

H o r Me) .32y33 Hydr idoal kene R=Ph, M=Os, R=Me) are formed by

reac t i on34 o f IPh3CI[PF61 i i t h [M(Me)2(PR3)(q-hmb)l, and t h e b a r r i e r t o ethene

r o t a t i o n i n [Os(Me)(CO)(n-ethene)(MegCp)l i s est imated35 t o be 47 kJ mol- l .

have been prepared; c y c l i c voltammetric s tud ies ,reveal an i r r e v e r s i b l e

one-electron o x i d a t i o n a t ambient t e m p e r a t ~ r e . ~ ~ Fragmentation pathways o f

The b i s a l l y 1 complexes [FeL2(n3-2-Me-C3H4l21 [L=PMe3, PMe'Ph, P(OMel31


OMe

C p Mo( CO), \

R' OO-.cN ( 3 ) R = H or Me

Ph \

( 5 )

H I ph\c&-i\ - c /OPh

I H'

( CO) F e - C =O

( 6 ) R = H,Me,OMe ,CI

Ph

Metal-Hydrocarbon n-Complexes 305

IFe(CO)L(NO)(n3-ally1 11 (L=CO or P-donor) have been investigated by mass spectro~copy~~ and a full report has appeared on the synthesis and fluxional properties of dinitrosyl complexes [FeL(N0)2(n3-al 1~111' (L=P-donor; allyl=C3H5, 1-Me-C3H4 or 2-Me-C3H4).38 Investigations have been made on the regio- and stereospecificity of carbanion addition to [Fe(C0I4(n -crotyl temperature addition of P(OEt), to [Fe(C0)4(~3-allyl 11' c o m p l e x e ~ . ~ ~ Syntheses of [FeR(C0I3(n3-C H )I (R= C-CH or N=CPh2) and [iFe-COCH2CH2NMe21(CO)2(q3-C3H5)l have been reporte;." The n1 :q3-acylallyl complex (41, prepared from KIFeinl -C (0 )CH=CHPh) (CO ),I and benzoyl c hl ori de , gi ves ( 5 1 upon t hermolysi s ; 42 treatment of [Fe(n -alkenyl )(CO)2Cpl complexes with LiMe followed by benzoylchloride affords [Fe(CO) (n3-a1 lyl )Cpl complexes .43 Binuclear [ O S ~ ( C H ~ C M ~ ~ ) ~ ( ~ I -C3H5I21 is synthesised by treatment of acetate bridged [Os,(CH2CMe3)4(u-02CMe)21 with44 Mg(C3H5)Br. Cyclopropenyl salts [C Ph Rl[BF41

and oxocyclobutenyl compl exes45 [Fe(CO 12( NO 1 (n3-C3Ph2RCO) 1 ; with phosphorus-donor ligands these complexes undergo carbonyl substitution or, cyclopropenyl ring expansion to oxocycl obutenyl s where R i. But.

3 and of low

I

1

3

(R=H, Me, But, Phl react with PPN[Fe(C0)3(NO)I to give [Fe(C0)2(NO)(q 33 -C3Ph2R)I

I 46

3 Coy Rh and Ir A series o f 5-coordinate complexes [Co(NCMe) (PMe3)3(n-alkene)l and

paramagnetic, tetrahedral [CO(PM~~)~(~-H~C=CHCN)I [BF41 have been reported47 and [CO(CO)~(NO) (n-1 -butene 1 I has been synthesi sed photolytical ly.27 Molecular orbital calculations of the reaction profile for the conversion of [Co(n1-CH2CH31 (PH3)Cpl to hydridoalkene [CoH(n-ethene) (PH3)Cpl implicate an intermediate with an agostic B-C-H+Co intera~tion.~~ Reaction of [C~(q-ethene)~CpI with RMgBr (R=Ph or ally1 1 yields respectively mixed metal compounds [Co(n-ethene )Cp( Ph )MgBr (TMED) I and [Co(n3-C3H5)CpMgBr (thf 1 21 ; crystallographic characterisation reveals the formation of Co-Mg bonds.49 Photolysis of [Rh(~~-ethene)~Cpl in appropriately doped liquid xenon affords5' [RhL(q-ethene)Cpl (L=N2 or CO); [Rh(CO) (q-ethene)Cpl participates in C-H and Si-H activation reactions.51 The structures of [IrMe(CO) (PPh3) (II-M~CO~CH=CHCO~M~)I~~ and [Rh(n-etheneI2(n-indenyl determined crystallographically and alkene rotation in the latter complex examined. to Rh(1) and Rh(I1) centres have been compared.54 Hydridovinyl complexes [IrH(q1-C2H3)(L)Cpl (L=CO, ethene) have been synthesised by photolysis of [Ir (q-ethene 12Cpl in low temperature matrices55 and the conversion of [Ir(phosphine) (n-ethene)Cpl to [IrH(n1-C2H3)(phosphine)Cpl has been examined by molecular orbital studies.56 The hydridoalkene [IrH(n-ethene) (PPrgi )Cpl+ is formed by reaction34 of [Ir(Me)2(PPr3i )cp] with [ph$][PF6] and

-

have been

Stability constants for 71 complexation of acyclic and cyclic alkenes


( 9 )

J

Ph

(11) * Pd Cy2

H l+ I

H

H - - 4 '

H H

(12)

/+ 1 ,CI 7"- CI

'R h

( 1 5 ) ( 1 6 )


[Ir(q-etheneI2(n-indenyl 11 has been synthesi sed and used as precursor t o several

i ndenyl i r i d i um compl exes. Reaction o f N ~ [ C O ( C O ) ~ I w i t h benzyl o r phenylacety l ha l i des a f f o r d s a

product m ix tu re which i nc ludes the r13-benzyl complexes (6).58 Treatment o f t he

c a t i o n i c a l l y 1 complexes [Rh(PMe3)(n -1,l-R -C H )(Me5Cp)lt (R=H o r Me) w i t h L i

B inuc lear n1 ,n3 -a l l y l br idged (71, formed by heat ing [Ir H(n -C3H5)(Me5Cp)l i n benzene, undergoes r e v e r s i b l e C-H o x i d a t i v e addi t i o d r e d u c t i v e e l i m i n a t i o n under m i l d thermal condi t ions.60 The cyclopropenyl complexes [Co(CO) (0 -C3Bu R2)1

~ y n t h e s i s e d ; ~ ~ r e a c t i o n o f oxocyclobutenyl [CO(CO)~(TI -C3Ph2HCO)I w i t h MeLi

under a CO atmosphere af fords61 pyrone ( 8 ) .

57

3

3 BEt3H g ives neu t ra l rhodocyclobutanes59 [ { R f+-b CR2CH2 H2)(PMe3) (Me5Cp)I.

and oxocyclobutenyl complexes [Co(CO),(q 3 -C3ButR2CO)1 (R=Ph, Bu 2 1 have been

3 t

3

- 4 N i , Pd and P t

[ N i Me(n-a1kene)CpI; thermolys is o f t h e n -diene complexes [ N i Me(n2-CH2=CR-CR'=CH2 )Cpl (R,R '=H o r Me 1 y i e l d s b i nuc l ear s - a - d i ene

complexes ( 9 ) t oge the r w i t h t h e corresponding s - t E - d i e n e isomers.62 A se r ies o f complexes [M(R2PCH2CH2PR2)(q2-butadiene)l (M=Ni, Pd, P t ; R=al ky l , a r y l ) have been prepared; c r y s t a l l og raph ic cha rac te r i sa t i on (M=Pd, R=Bu 1 revea ls an

s-trans-butadiene l igand.63 Monoaza-l,3-dienes (mad) r e a c t w i t h

[ N i (PPh3I2(v-ethene)l t o g i v e [ N i (PPh3I2(n -PhCH=CHCH=NR)I (R=alkyl, a r y l ) ;

c r y s t a l l o g r a p h i c c h a r a c t e r i s a t i o n (R=Ph) revea ls n2-(C=C) coo rd ina t i on o f t h e mad 1 igand which adopts an s - t rans conformation.64s65 Ethene complexes

- cis-[PtMe2(SMe2) (TI-ethenell and [{PtMe(n-ethene) (u-Cl )),I have been prepared; t h e l a t t e r r e a d i l y exchanges ethene f o r o the r alkenes o r alkynes.66 The

k i n e t i c s o f f o rma t ion o f trans-", a1 kene) [{Pk-OC(0)-CH2CH2hH2~Cl (n -e thene l l from K[PtC13(n-ethene)l and the anion o f B-alanine have been i n ~ e s t i g a t e d ~ ~ and

t h e r e l a t i v e s o l u t i o n s t a b i l i t i e s o f a se r ies o f complexes

t rans- [PtCl 2py(n-al kene) l have been measured us ing ' H nmr spectroscopy.

[ {Ni (n3-Z-(CH SiMeg)C3H4) ( ~ - 6 r ) ) ~ I prov ides a r o u t e t o f u n c t i o n a l i s e d

Ph) and [Pd(n3-l -w-Ph-C3H4)Cp1 have been prepared; c r y s t a l l og raph ic cha rac te r i sa t i on revea ls an asymmetry i n Pd-a l ly1 bonding.18 Reaction o f

IPd(PPh3)2(n3-C3H5)lt w i t h K[02Butl affords7' t h e peroxo complex [Pd(02But)(PPh3)(n3-C3H511. Binuclear methylenecycloal k y l complexes (10) have been prepared f rom [{Pd(NCMe)2(u-C1 ) I 2 ] and methylenebicyclo[n. l .O . l alkanes and t h e e f f e c t s o f r i n g s i z e on t h e =-anti i somer i sa t i on o f exocyc l ic n - a l l y 1

complexes i n ~ e s t i g a t e d . ~ ~

Reaction o f NiCp2 w i t h MeLi i n t h e presence o f a v a r i e t y o f alkenes g ives 2

t

2

68

Reaction o f organic ha l i des w i t h t h e i s o l a b l e s i l y l a l l y l complex

a l l y l ~ i l a n e s . * ~ A l l y 1 complexes [Pd L2 (n 3 -l-syn-R-C3H4)l (L2=cod, TMED; R=Me o r

Several r l q l y l pa l lad ium complexes have been


prepared by o x i d a t i v e a d d i t i o n o f a l l y l a r y l e t h e r s , a l l y 1 a lcohols and

N-a l ly lamines t o [Pd(PCy3),1; [Pd(Ac)(PCy3)(n -C3H5)l, formed by r e a c t i o n w i t h

a l l y l a c e t a t e , r e a c t s w i t h nuc leophi les t o y i e l d b inuc lea r

[Pd,(PCy,),(p-Ac)(p-C3H5)l. a f fo rds (11) v i a t h e mononuclear in termediate [Pd(SPh) (PCy3)(n -C3H5)l; t h e decreased r a t e s o f analogous reac t i ons w i t h y -subs t i t u ted CHR=CH-CH -SPh (R=Me

o r Ph) suggest a t tack o f Pd a t C(y) as t h e r a t e determin ing step.732 K i n e t i c

isotope e f f e c t s tud ies i n d i c a t e t h a t format ion o f (12) f rom PdC1, and

3 72

Ox ida t i ve a d d i t i o n o f CH2=CH-CH2-SPh t o [Pd(PCy3).$ 3

methylenecyclohexane proceeds v i a n-comp

base-induced proton removal . 7 4 R e a c t i on

subs t i t u ted d e r i v a t i v e s w i t h [PdClZ(NCPh which, i n so lu t i on , rearrange t o n 3 - a l l y [ P d 2 { q 3 - C H 2 ~ C R ~ C H ( C H 2 C H 2 C 1 ),(p-Cl ),I [ML2(n3-a l ly l 11' (M=Pd, P t , L=phosphine;

L

exa t ion o f Pd w i t h subsequent o f v iny lcyc lopropane and some

2l a f f o r d s r ing-opened complexes (13)

R=H, Me, P F - C ~ H ~ ) . ~ ~ The reduc t i on o f complexes

M=Pd, L=NCMe o r L2=diene) has been

inves t i ga ted both e lec t rochemica l l y and by reac t i on76 w i t h LiBEt3H.

3-chl oro-2-chloromethyl prop-1 -ene and [ P t ( PPh3l41 o r [ P t ( PPh3 ,(n-ethene) 1 i n [Pt(PPh3)2(n3-2-(CH2C1 )C3H4)l[PF61, prepared f rom

t h e presence o f K[PF61, e x h i b i t s an act ivated-carbon-chlor ine bond which f a c i l i t a t e s synthes is o f [Pt(PPh 1 {I-I -2-(CH2L)C3H4)1[PF61 (L=PPh3, NEt3, py,

B r ) and t h e b r i d g i n g tmm C O ~ ~ ~ ~ X ~ ~ ~ [ P ~ ( P P ~ ~ ) ~ { ~ I ~ - C H ~ C [ C H P t C l (PPh3)21CH2)1[PF I 32 786 * T r i a l l y l a r s e n i t e As(O-CH~-CH=CH,)~ a f f o r d s [Pt(PPh ),(?-I -C3H5)l on r e a c t i o n

w i t h [Pt(PPh3)31 and i n p o l a r media [ { P m R } C l ( n l - C H 11 (R=Me, Ph) i s r a p i d l y converted7' t o c a t i o n i c [{f't-PPh,CH2CH2kR,[n3-C3H5)l . Treatment o f

[ N i (n-codl21 w i t h cyc lopropenyl s a l t [C3Ph31Br a f f o r d s c r y s t a l l o g r a p h i c a l l y

cha rac te r i sed [C3Ph31 [ {Ni (n3-C3Ph3) 12( p-Br l31 ; r e a c t i o n o f [NiL2(n-cod) 1 (L2=bisphosphine) w i t h [C3Ph31Br yields8' [NiBrL2(n-C3Ph3)1.

3

+3

5 Other Metals and Theoret ica l Studies

A t -80°C [T iCl (q- indenyl ) , I r eac ts w i t h MeMgCl and ethene t o g i v e t i tanacyc lopentane [ { T i -CH2CH2CHfCH2)(n-indenyl ),I which, on warming t o -2O"C,

affords, r e v e r s i b l y , ethene and8 [T i (I-I-ethene)(n-indenyl ) , I . Elec t ron impact and chemical i o n i s a t i o n mass spect ra o f [T i (rl - a l l y 1 )Cp21 complexes are reported82 and hyd r idoa l kene complexes [TaH(n-al kene) (Me5Cp),1 have been

synthesi sed. 3

complexes (M=Mn, Re) have been i n ~ e s t i g a t e d ~ ~ and t h e agos t i c C-H-tMn

i n t e r a c t i o n i n [Mn(C0I3(n -cyclohexenyl 11 has been s tud ied by photoelect ron s p e c t r o ~ c o p y . ~ ~ The hyd r idov iny l complex [ReH(nl -CH=CH2) (PMe3l2Cp1 isomeri ses85 a t 20°C t o [Re(n-ethene) (PMe3l2Cp1 and t h e mes i t y lox ide complex

[Re(CO) 2(n -Me2C=CHCOMe 1 (Me5Cp) 1 has been synthes i sed and cha rac te r i sed

- - 3

83

Elec t ron impact and chemical i o n i s a t i o n mass spect ra o f [M(C014(n - a l l y 1 11

3

2

Metal-Hydrocarbon n-Complexes

H

(17)

H \ C / H - R h ( a c

a c a d R h

>( R '

a c )

Ph,

Me (cod) Rh

'P

Ph2

(18)

309

1 *+

(19) R I R'= a l k y l (20 )

R C= C/

R\

(21) M = R h , I r j R = C02Me ( 2 2 1

Ph CP /

(23 1


c r y s t a l l o g r a p h i c a l l y . 8 6 Formation constants o f a se r ies o f new complexes

[CuL(n-al k e n e l l (L=bipy o r phen) have been determined spectrophotometrically.87 Extended Hdckel methods have been employed i n s tud ies on t h e conformation

o f cis- carbene-a1 kene complexes8* and t o compare t h e bonding c h a r a c t e r i s t i c s o f

II - v i n y l and TI -keteny l l i gands w i t h those o f f ou r -e lec t ron alkyne l igands. Cotton-Kraihanzel carbonyl s t r e t c h i n g f o r c e constants i n complexes [LnM(CO)l may

be used t o p r e d i c t t h e r e a c t i v i t y o f [LnM(q-ethene) I analogues towards

nuc leoph i l i c a t tack a t ethene.”

2 2 89

- C Complexes Der ived f rom Uncon jugated Dienes - 1 Fey Ru and 0s

[RuH(n-cod)Cpl, synthesised f rom [ R ~ H ( N H ~ N M e ~ ) ~ ( r l - c o d ) l [PF61 and TlCp,

e x h i b i t s f a c i l e H m i g r a t i o n t o t h e cod r i n g , thus r e a c t i o n w i t h PPh3 a f f o r d s [Ru(PPh3) (n3-cyc loocteny l ICpI bu t w i t h dppm t h e a1 kenyl complex

[Ru(dppm)(n -cyc loocteny l )Cp] i s formed; t h e l a t t e r complex e x i s t s as two

isomers due t o r e s t r i c t e d r o t a t i o n about the Ru-cyclooctenyl bond.91

o f [RuH(~-cod)Cpl w i t h CC14 g ives [RuC1(11-cod)Cpl which i s a precursor t o [RuC1L2Cpl (L=phosphine, L2=diene), [RuL3Cpl [PF61 (L=CO, L3=n 6 -po lya lkeneIg2 and

c y c l i c a l l y 1 complexesg3 such as (14) .

“H41 [PF61 y i e l d s [Ru(n6-cyc lo-octa- l ,3,5-tr iene)Cpl [PF 1 via t h e c r y s t a l l o g r a p h i c a l l y cha rac te r i sed in termediate (15) .

1

Treatment

Reaction o f [RuCl(q-cod)CpI w i t h excess

946

2 Co, Rh and I r

a f fo rds [Rh L2(diene)31RhCl ( d i e n e l l o r [RhC1L2(diene)l (L2=en, TMED,&.

- Reaction o f [ {Rh(d iene)(u-Cl )I2] (diene=cod, nbd) w i t h a l i p h a t i c diamines

and s i m i l a r s tud ies have been made on reac t i ons o f 2,2’-dipyridylarnine w i t h [{M(diene) (v-Cl ) I 2 ] (M=Rh, Ir; diene=cod, nbd, tetraflurobenzobarrelene) .96 Crysta l s t ruc tu res o f [Rh(rl-cod) ( 2 , 6 - d i a l l y l p y r i d i n e ) I [CuCl2Ig7 and the asymmetric hydrogenation c a t a l y s t s ( l 6 I g 8 and [Rh(q-nbd) (R-d ibutphos) l [C1O4Ig9 [d ibutphos=(17)1 have been determined. Syntheses o f t h e enan t iose lec t i ve

hydrogenation c a t a l y s t (18)’00 and o f [M(n-cod)(vCF3Cp) l (M=Rh, I r I 1 O 1 have

been repor ted. l-methylene-4,4-dial k y l -cyclohexa-2,5-dienes a f f o r d s l o 2 b inuc lea r complexes

Treatment o f [Rh(acac)(n-ethene)21 w i t h

(19); r e l a t e d reac t i ons w i t h cyclohexa-2,5-diene-l-ones have a l so been

invest igated.

by r e a c t i o n o f [ R ~ ( H ) ~ ( d p p m ) ~ I w i t h [{M(q-cod)(u-Cl )I2]; t reatment o f t h e rhodium complex w i t h H[BF41 a f fo rds [Ru(dppmI2(u-H) (u-Cl )Rh(n-cod) l w h i l s t reac t i on w i t h MeLi y i e l d s phosphido br idged (20) .104y105

[{Rh(n-cod) 12(p-C1 1 (u-PBut2)] has been synthesised and cha rac te r i sed

103

Binuc lear [RuH(dppm)(u-H)(u-Cl ) (u-dppm)M(~~-cod) l (M=Rh, I r ) i s synthesised

Phosphido br idged

Metal-Hydrocarbon z-Complexes 31 1

c r y s t a l l o g r a p h i c a l ly; lo6 alkynes reac t w i t h [(M(n-cod) (u-PPh2)121 (M=Rh, I r ) t o

g i ve lo7 c i s -d ime ta la ted alkene complexes (21 1. A se r ies o f i r i d i u m hydr ido diene complexes [ I r H L 2 ( d i e n e ) l (L=P-donor

l igand, diene=cod o r tetrafluorobenzobarrelene) which are a c t i v e H- t rans fe r

cata lysts , lo8 and [ I r (Hl2(SiEt31(EPh3) (n -cod ) l (E=P or As), a c t i v e i n t h e dehydrogenative s i l y l a t i on o f a1 kenes ,’ O9 have been prepared. Treatment o f

[ { I r ( n - c o d ) (u-Cl )I2] w i t h PMe3 af fords ’ ” t r a n s - [ I r C l (PMe3)2(n-cod)3, and t h e tetrafluorobenzobarrelene ( t f b ) complexes [ I r ( B - d i ketonate) ( n - t f b l l and

Reaction o f [Ir(o-PPh2C6H4NHR)Cl (n -cod ) l (R=Et, CH2Ph) w i t h Ag[C1O41 a f f o r d s

chelated complexes [ { f r o-PPh2C6H4kHRl(n-cod)1 [C1043; thermolys is o f t h e benzyl

d e r i v a t i v e gives1” cyc lometa l l a ted (22). o f [ { I r (n -cod ) (u -C l )121 w i t h MeLi i n t h e presence of PhCXPh.

r e v e a l i n g two d i s t i n c t one-electron oxidations,’ l4 and by picosecond spectroscopic techniques t o probe s i n g l e t and t r i p l e t e x c i t e d s ta tes .

Heterobimetal 1 i c phosphido br idged complexes [M(CO),(u-PPh2 I 2 I r H (n-cod 11 (M=Cr , Mo, W , ~ = 4 ; M=Fe, ~ = 3 ) have been synthesised from [T I r (n -cod ) (v-Cl ) I 2 ] and L i [M(CO),( PPh2H 1 ( PPh2 I . 116

[ I r ( B-di ketonate-C3)L2(n- t fb) 1 (L2=bipy, phen) have been synthesi sed. 111

Complex (23) i s formed by t reatment 113

Binuc lear [ ( I r ( n - c o d ) (u-pyrazoly l )I2] has been s tud ied e lect rochemical ly ,

115

- - 3 Ni, Pd and P t

Reactions o f [ P t C l (n-cod) ] w i t h MeLi o r [(PtMe2(u-SMe2)121 w i t h cod p rov ide improved

PPh3 w i t h [Pt (Ph)(n l -Cp)(n-codl l . K i n e t i c s tud ies reveal a two s tep process i n format ion o f IPdC12(n-diene)l complexes f rom Na[PdCl2(0CMe2)I and t h e

appropr ia te diene;T19 t h e k i n e t i c s o f n u c l e o p h i l i c a d d i t i o n t o cod i n

I M B r 2 ( ~ - c o d ) l (M=Pd, P t ) are s t rong ly metal dependent.’“ A se r ies o f

[PtMe(nucleoside 1 (n-cod 1 I -t complexes have been synthesi sed.

t o [Pt (Me)2(n-cod) l ; (24) i s formed by r e a c t i o n 1 l 8 o f

121

4 Other Metals [Mo (CO 1 2{~4- 2,3- ( d i carbomet hoxy 1 nbd 121 has been

c r y s t a l l og raph ica l 1y. l 22 Co-condensation o f Re atoms and 1,5-cod g ives [Re(Ph)(r~-cod)(n-C,H~)I and t h e cyc

[Re(n -C Hqq)(n-C6H6)l; o n l y the l a t t e r i s formed i f 1 ,5 -c0d . ’~~ Formation constants o f [(CuCl (d iene)121

measured.

-

5

124

c harac t e r i sed w i t h a m ix tu re o f benzene

ooctadi eny l complex ,3-cod i s used i n p lace o f

diene=cod, nbd) have been

- D

- 1

Cornpl exes Der ived f rom Conjugated D i enes

C r , Mo and W A se r ies o f paramagnetic, c y c l i c diene complexes [Mo(X)2(q-diene)Cp]


(X=Br, C1 , S-a ry l ) have been synthesised and s tud ied by esr spectroscopy and

c y c l i c ~ o l t a m m e t r y . ’ ~ ~ A t 0°C reduc t i on of [ { M O I ~ ( N O ) C ~ ) ~ I i n t h e presence o f

diene (diene=ZY3-dimethylbutadiene) a f f o r d s an isomer ic m ix tu re o f [Mo(N0)(n4-cis-diene)CpI and [Mo(NO)(n4-trans-diene)Cpl i n a 4 : l r a t i o ; t h e

- cis-d iene k i n e t i c product has been character ised c r y s t a l l o g r a p h i c a l l y and t h e

thermodynamic s t a b i l i t y o f t h e t rans-d iene conformation r a t i o n a l i s e d by molecular o r b i t a l calculations.-Treatment o f MoC15 o r WC16 w i t h anthracene-activated Mg i n the presence o f diene (d iene=lY3-butadiene and methyl

subs t i t u ted d e r i v a t i v e s ) y i e l d s [M(n -dienel31 (M=Mo, W) . l Z 7 Photo lys is o f

[ M O ( C O ) ~ { ~ ’ ,r15-(C2H4)Cpll w i t h lY3 -bu tad iene and i t s methyl s u b s t i t u t e d d e r i v a t i v e s g ives complexes such as (25);128 s i m i l a r l y dienes r e a c t w i t h the acety l complex [Mo(COMe) (n4-cyclopentadiene)Cpl t o g i v e eny l ketone complexes such as (26) via displacement o f cyclopentadiene and subsequent coupl ing o f

d i ene and ace ty l 1 igands .’ 29 The quasi square pyramidal compl exes [W(COMe)(CO)(n4-diene)Cpl, synthesised by p h o t o l y s i s o f [W(Me)(C0)3Cpl w i t h a c y c l i c o r c y c l i c dienes, e x i s t as two isomers i n which t h e te rm ina l carbons o f t he conjugated d iene system p o i n t towards o r away f rom t h e Cp r ing. ’30 The synthesis, geometry and dynamic p roper t i es o f a se r ies o f [ W (C0)3{P(OMe l31 (n4-d i ene 1 I complexes have been i nves t i gated;’ 31 a

4 stereochemical s tudy o f [W(C0l4(rl - lY4 -d ipheny l -1,3-butadiene)l has a l so been

made.132 Pho to l ys i s o f [Mo(C0)3(n1-pentadienyl )Cpl induces sequent ia l formation133 o f [ M O ( C O ) ~ ( Q ~ - S n pentadienyl )Cpl and [Mo(CO) (r15-pentadienyl ICpI.

subs t i t u ted cyc lopentadieny l complexes’ 34 [ C r (C0)3{r15- (CMe2Y ) C p l l - Rate

constants and a c t i v a t i o n parameters have been determined f o r Cr(C0) m iq ra t i on f rom the e i g h t t o t h e six-membered r i n g o f benzocyclooctatetraene. [M(C0)3(NCMe)31 (M=Cr, Mo, W) induces i somer i sa t i on o f (27) t o (28) ; [Cr(C0)31n6-(28)11 has been character ised ~ r y s t a l l o g r a p h i c a l l y . ~ ~ ~ The complexes [M(COI3ln - ( 2 9 ) l 1 (M=Cr, Mo) have been synthesised; two a l t e r n a t i v e modes o f bonding between Mo and ( 2 9 ) are observed.137 [ C r 2 (CO 1 6( n6,n6-heptaful va l ene 11 reac ts photochemical l y w i t h butadi ene t o g i ve (30) y& successive [4+61 cyc loadd i t i ons and decomplexation;138 s i m i l a r s tud ies

are repor ted on t h e c y c l o a d d i t i o n o f butadiene and i t s methyl s u b s t i t u t e d d e r i v a t i v e s to139 [Cr2(CO)61r16,~6-1 ,1 ‘ - b i (2,4,6-cycloheptatrien-l-yl)ll. The

e l e c t r o n i c s t ruc tu res and r e a c t i v i t i e s of cyc lohep ta t r i eny l complexes [M(CO),(rl-C7H7Ilf (M=Cr, Mo, W) have been examined by molecular o r b i t a l methods140 and t h e r e s u l t s o f t h i s work app l i ed t o t h e r e a c t i o n o f [M(COl,(n-C,H,)I+ w i t h a1 koxide ions, t h e subject o f two recen t studies.141 y142 Several cyc l o h e p t a t r i enyl molybdenum complexes have been cha rac te r i sed by 95M0

n.m.r. s p e c t r ~ s c o p y ’ ~ ~ and t h e spectroscopic p r o p e r t i e s and some reac t i ons o f

4

+- Reaction o f [Cr(CO),(rl -6,6-dimethylfulvene)l w i t h nuc leophi les Y - a f f o rds

t3J

6


(27)

( 2 9 )

77 7=* ( PMe ’ 3Fe 0

(31 )

(28 )

( 3 0 )

U (32)


[WI (CO)2L2(n3-C7H7)I (L2=dppm, dppe) have been r e ~ 0 r t e d . l ~ ~

2 Mn and Re

R=H, Me) have been synthesised; s o l u t i o n dynamics and c r y s t a l l o g r a p h i c s tud ies are a l so reported.145y146 Treatment o f [MnR(C0)2(n-benzene)l (R=a lky l ) w i t h

phosphines a f f o r d s a l k y l m i g r a t i o n products [Mn(CO I2(phosphi ne 1 (r15-endo-R-cycl ohexadienyl 1 I . Reaction o f [Re(H 17( PPh3l21 w i t h benzene and i t s methyl subs t i t u ted d e r i v a t i v e s i n t h e presence o f 3,3-dimethyl butene g i ves complexes [Re(H) 2 ( PPh3) 2(n -cyclohexadienyl I which

a f f o r d [Re(HI3(PPh3l2(n -cyclohexadienyl 11’ complexes on treatment148 w i t h HIBF41 or, [Re(H)2(PPh3)2(n6-arene)l’ with149 [Ph3CI[BF41. K i n e t i c s tud ies on nuc leoph i l i c a d d i t i o n t o cyclohexadienyl complexes IMn~CO)L(NO~(1-5-r1~-6-R-cyclohexadienyl )It (L=CO, phosphine; R=H, Me, Ph, CN)

reveal an R dependent r e a c t i o n rate;150 an analogous study w i t h [Mn(CO)L(NO) (l-5-~5-6-R-cycloheptadienyl ) I t complexes has been made151 and these

l a t t e r reac t i ons app l i ed i n t h e synthes is o f d i f u n c t i o n a l i s e d cycloheptadienes.’ 52

- A se r ies o f complexes [M(phosphine13(n5-2,4-R2-pentadienyl 11 (M=Mn, Re;

147

5 5

- 3 Fey Ru and 0s ( a ) Acyc l i c Dienes

Ultrasound promotes t h e format ion o f [Fe(CO)3(n - d i e n e ) l and

[Fe (CO 3( n4-tmm) I f rom [Fe2(C0 ),I and t h e appropri a t e hydrocarbon. 53 Reaction o f FeC12 w i t h Mg butadiene P th f and P E t 3 affords [Fe(PEtq) ( r i -butadienel l which

i s precursor t o severa l [Fe(PEt3)(n-diene)21 ~omp1exes;~‘~~treatrnent o f [Fe(PMe3)3(ri-butadiene) 1 w i t h C02 g ives c r y s t a l l og raph ica l l y cha rac te r i sed (31 1 , which i s a precursor t o mono- and d i ca rboxy l i c acids.155 New syntheses o f

[Fe(C0)3(n-2-formylbutadiene)l and i t s reac t i ons w i t h carbanions are d e ~ c r i b e d ; ’ ~ ~ unprecedented 1,4-diacyl a t i o n o f t h e complexed d iene resu l t s157 from F r i e d e l -C ra f t s acy l a t i on o f [Fe(CO )3{n4-2- (S i R3 1 -butadi e n e l l . Carbani on (32) reac ts w i t h e l e c t r o p h i l e s t o g i v e e i t h e r l Y 3 - d i t h i a n e d i e n e complexes o r t r i m e t h y l enemethane complexes.’ 58 I n s o l u t i o n [Fe(C0I2( PPh3) (n-d iene) I complexes e x i s t as isomer ic mix tures w i t h PPh3 i n t h e a x i a l o r basal p o s i t i o n o f t he square pyramidal s t ructure.159 Reaction of benzylideneacetophenone and i t s

subs t i t u ted d e r i v a t i v e s w i t h [Fe3(C0)121 g ives 1 -aroyl-2,4,5-tr i a r y l c y c l opentenes v i a [Fe (CO 1 3( n -enone) I complexes.

and t rans-1 -chloropenta-2,4-dieneY induces sequenti a1 format ion ’ 61 o f [Fe(CO)(n -syn-pentadienyl )Cpl and [Fe(q -pentadienyl ICpI. t rans-1 -bromopenta-2 , 4-di ene w i t h [Fez (CO 1 ,I a f fo rds

4

4 160

Pho to l ys i s o f [Fe(C0)2(n1-pentadienyl )Cpl, synthesised f rom Na[Fe(CO).$pl

3 5 Reaction o f

Metal-Hydrocarbon rr-Complexes 315

(331 R = H

( 3 4 1 R = Me

Ph

( 3 8 )

Q I

9; CH,Ph

I Ru ph3- Ph ,* Ph

R

(351 R = H , C H O

(CO I3Fe -Fe(CO),

(371

1+ Fe(CO1, P(OPh1,

. ‘(CH2I2OA c

(39 1

Q F2

Si \

F2

(41)


[FeBr(C0)3(r, 3 - 2 - p e n t a d i e n y l l l ; r educ t i on w i t h Zn

[Fe(CO 1, ( n4-1 -methyl bu tad i ene) 1 and ( 33 1’ 62 whi 1 s t

powder g ives

reduc t i on o f

[Fe(CO )j(r,5-2,4-dimethyl pentadienyl I + y i e l d s (341.’ 63 Treatment o f [RuHCl (PPh3l31 w i t h penta- lY4-d iene g ives [RuCl (PPh3I2(r, -pen teny l ) ] which undergoes sequent ia l d e h y d r ~ g e n a t i o n ’ ~ ~ t o [RuCl (PPh3l2(q5-pentadienyl 11 and

[RuCl (PPh ) Cpl. prepared1252from t o s y l a t e o r t r i f l a t e s a l t s o f [Ru(H20),l2+. Complexes (35) behave as masked r, , n (3e- I -butadieny l complexes i n t h e i r reac t i ons w i t h P(OMeI3 and PhCzCPh.166 The trimethylenemethane l i g a n d precursor 2[(methylsulphonyloxy)methyl l-3-tr imethyl s i l y l p rop -1 -ene has been employed i n the syntheses [ M C l (NO)(PPh3) (n4-tmm)l (M=Ru, 0s ) and

10s (CO l 2 ( PPh3 1 (n4-tmm) 1.

3

5 Mixed sandwich complexes [Ru(r, -d ieny l (n-arene)]’ have been

1 2

( b ) Cyc l i c Dienes The b a r r i e r t o r i n g r o t a t i o n i n [Fe(C0I3(r, - cbd ) l has been determined 4

us ing Proton Sp in -La t t i ce r e l a x a t i o n t ime measurements and v i b r a t i o n a l spectra, ’ 68 Reaction o f l Y 2 , 3 - t r i phenyl-3-vinylcycloprop-1 -ene w i t h IFe2(C0)91

a f fo rds (36) ,’ 69 and d i hydroacepental ene compl exes such as (37 have been

s y n t h e ~ i s e d . ’ ~ ~ Molecular o r b i t a l s tud ies have been made on Fe(C0I3 complexes o f para-qui nodimethane and re1 ated conjugated hydrocarbons,’ 71

[Fe(CO )3(r,5-cycl ohexadi enyl 1 It, forming the acyl i o d i d e

[Fe(COI )(C0)2(~5-cyclohexadienyl ) I , competes w i t h a t tack a t t h e d ieny l r ing;17* f l u o r i d e i o n r e a c t s w i t h [Fe(C0)3(r, - cyc lohexad ieny l ) l+ t o g i v e (38). K i n e t i c s tud ies have been made on the mechanism o f 2 -e thy lpy r id ine a d d i t i o n t o

IFe(C0)3(r i5-dienyl 13’ compl exes.’ 74 Oxidat ive cyc l i sa t ion of pr imary a lcohol

groups onto [Fe(COl2L(r,-diene) 1 [L=CO, d i ene=chd; L=P(OPh 13, diene=cycloheptadienel g i ves c y c l i c e the r products. Ring opening, induced by treatment w i t h a c e t i c anhydride, a f fo rds s t e r e o s p e c i f i c a l l y subs t i t u ted

complexes such as (39) which undergo s tereo- and r e g i o s p e c i f i c n u c l e o p h i l i c a d d i t i o n t o y i e l d cis d i s u b s t i t u t e d s i x - and seven-membered r ings.175 cyclohexadienyl complex formed by redox-induced hydr ide abs t rac t i on f rom exo subs t i t u ted (40) , undergoes s tereo- and reg iospec i f i c nucleophi 1 i c addit ion.’ 76 4-vinylcyclohexenes isomer ise on treatment w i t h Fe(COI5 t o g i v e complexes [Fe(CO)3(r,4-R-chdJ1 (R=alky l

cyclohexadiene t o 1,1,2,2-tetrafluoro-1,2-disila-3-Bu -cyclobut-3-ene proceeds v i a i s o l a b l e (41). ’78 Cocondensation o f Fe atoms w i t h 1,3- o r 1,4-chd i n argon

matr ices a f f o r d s [Fex (chd ) l ( x = l o r 2). [Ru(CO) (n3-cyclohexenyl 1 (n5-cyclohexadienyl 11 , synthesised by cocondensation o f

Ru atoms w i t h 1,3- o r 1,4-chd fo l l owed by C O Y rearranges the rma l l y t o

I n acetone o r nitromethane, a d d i t i o n o f i o d i d e i o n t o a carbonyl l i gand o f

5 173

The

the Fe(C0I5 induced cyc loadd i t i on o f t

179


(42)

N& / I

(46 1 R

I / Ru( CO12L

(181

1+

1'

( 47 1 M = Ru( CO),PPh, >?7M?Mt Me

Co( PMe,),

( 4 9 ) M = S i , G e

1 2+


[Ru(CO)(n4-chd),1 and forms [Ru(C0)(q3-cyclohexenyl )(I16-C6H6)lt by reaction 180

with [Ph3CI [BF41.

defined cis-1 , 3 - d i r n e t h y l c y ~ l o h e p t a d i e n e ~ ~ ~ and chiral recognition is displayed in the reactions of [Fe(CO)2{P(OPh3) I (n5-cycloheptadienyl 1 It with sulphoximi ne stabi 1 i sed enol ates . 82 Reaction of [FeMe(CO 1 (n5-cycl ohept adi enyl 1 I wi th CO affords endo-acyl ated (42); the probable intermediate183 is [Fe(COMe (CO 2( n5-cycl ohept adi enyl 1 I . The synthesi s , stereochemi stry and

4 reactions of acylcycl oheptatriene complexes [Fe( CO 1 3{ 1 -4-II -7- (COR) -chpt 11 has been r e ~ 0 r t e d . l ~ ~ Cycloaddition of TCNE to IFe(C0)3(~4-chpt)l gives (43) as the major primary product; the kinetics and mechanism for thermal conversion of (43) to (44) have been in~estigated’~~ and complex (45) adds two equivalents of TCNE in a stepwise, reversible manner.186 Nmr studies reveal that the diastereomeric isomers of [Fe(C0)3{x-y-n4-2-(OR)-troponeIl (x-y = 2-5 or 4-7; R=Ac, SiMe2CHMeEt group.187 Ring conformations and rotation barriers in the complexes

5 [Fe(C0I3(n -dienyl)I (dienyl = cycloheptadienyl, cyclooctadienyl) have been investigated by molecular oribtal methods.188 Reaction of either cyclohepta-lY3-diene or chpt with [RuHCl (PPh3l31 affords18’ [ RuC 1 ( PP h3 1 ( n5-cyc 1 ohept adi enyl 1 1 .

which isomerises on warming to yield, sequentially, [RuH(n -cyclooctadienyl ),If then 16-electron [Ru(n4-l ,3-cod)(r15-cyclooctadienyl~l~; reaction of (46) with pentamethyl cycl opentadiene affords’ One-electron oxidation of IR~(CO)~(PPh~)(rl~-cot)l gives (47 via C-C bond

[R~(CO)~L(rl~-cot)l (L=CO, PPh3) with [Fe{P(0Me),I(NO),(n3-a 1 ~ 1 1 1 ’ gives (48) whilst reaction with [Fe(C0)3(~5-cyclohexadienyl 11’ affords bimetallic [ R U ( C O ) , L ( ~ ~ , ~ ~ - C , H ~ { F ~ ( C O ) ~ ( ~ ~ ~ - C ~ H ~ ) I I ~ 2 C-C bond coup1 ng of six- and eight-membered rings.192 The photochemistry of [M(q5-C5R5) ri6-cot1lf and [ML(n4-cot)(q5-C5R5)1+ [R=H, Me; M=Fe, Ru; L=CO, P(OMel31 has been examined. 193

[Fe(C0)2{P(OPh I3I (n4-cycloheptadienel I i s a precursor to stereochemical ly

interconvert y-& a lY3-haptotropic rearrangement of the Fe(C0I3

4 6 Low temperature protonation of [Ru(rl -cod) (rl -cyc7ooctatriene)l gives (46) 5

[RuH(a5-cycl ooctadi enyl )Me5Cplt.

co~pling”~ o f the radical cation [Ru(CO)~(PP~~) (II 4 -cot)]+; treatment of

- 4

by sequential double nucleophilic additionlg4 to [Co(CO) (~~~-butadiene)l[BF~l. Stereochemical labelling studies have been made on [CO(II -diene)Cpl (diene=butadiene and substituted derivatives) to probe the mechanism of substituent exchange at the terminal diene carbons.lg5 Treatment of N~[CO(CO)~I wi t h trans- 1 - bromopen t a- 2,4-d i ene affords’ 96 [Co ( CO r e a c t x o f [{Rh(PR3)2(p-C1 1 121 (R=al kyl with K[2,4-dimethylpentadienidel

Coy Rh and Ir Regio-and stereospecific 1,4-difunctionalisation of butadiene is effected

a

( n3- syn-pen t adi eny 1 1 I i

Metal-Hydrocarbon n-Complexes 3 19

yields 16-electron complexes [Rh(PR3)2(n3-2y4-dimethylpentadienyl 1 I with a predominant anti-pentadienyl conformation.lg7 Substitution reactions and redox chemistry of [Co( PEt3 )2(n5-2,4-dimethyl pentadi enyl 11 have been investigated and crystal lographic studies reveal a redox-dependent conformation of [Co(PMe 1 (n3-2,4-dimethylpentadienyl )I2 (z=O, n3-@; z=tl s 3 - x ) . [Rh(n -1 -phenylpentadienyl )Cpl [PF61 has been crystallographically characterised and its reactions with halide ions investigated;lg9 attempts to synthesise a pentadienyl complex by reaction of [Coln4-2,4-bis(trif1uoromethy1 )penta-ly3-diene1Cp3 with [Ph3Cl [BF41 give [Co(n5-triphenylmethyl )Cpl [BF41. The trimethylenemethane complexes [MCl(PPh3)2(n4-tmm)l (M=Rh, Ir) and [IrX(CO)(PPh3)(n -tmm)l (X=Br, C1) have been synthesi sed.

Treatment of ~Co(C0),(n4-Me4cbd)l [PFs] with Na[M(C0)3Cpl (M=Mo, W ) affords bi nuclear complexes [Co(CO) (n4-Me4cbd 1 (LI-CO)~M(CO) 2Cpl which are converted thermally201 to [Co(s4-Me4cbd) (U-CO)~MC~I (Co=M). Metallole complexes (49) are formed by reaction of [CoBr(PMe3l31 with the appropriate metallole in the presence202 of Na[BPh41. Variable temperature n.m.r. studies on [M(n-6,6-diphenylfulvene) (n-cod)l+ (M=Rh, Ir) provide evidence for an intramolecular rearrangement involving rotation of the diphenylfulvene 1 igand.203 The redox chemistry of [Co(s4-chpt )Cpl, CCo(n4-cycloheptadienelCpl

5 and the cycloheptadienyl complex [Co(n -C7H9)Cpl+ has been investigated; reduction of the latter complex gives a neutral radical which slowly dimerises to [Co Cp (n4,n4-C1 4H1 8) 1 via C-C bond coup1 i ng between two cycl oheptadi enyl rings.*042 The kinetics of interconversion between neutral

corresponding monoanions, have been investigated by n.m.r. and electrochemical methods.205 Complex (501, which exhibits a unique example of a 1,4-n2-bonded perfluoro-cot ligand, has been synthesised and characterised crystal lographical ly.

198 5 3 3

200

4 167

[Co(l-4-n4-cot)(C5R5)l and [C0(1,2; 5,6-n 4 -cot)(C5R5)l (R=H, Me), or between the

206

- 5 Other Metals Reaction of vinyllithium with [MC12Cp21 (M=Zr, Hf) gives

[M(q4-butadiene)Cp2]; with MC14 (M=Ti, Zr, Hf) in the presence of dmpe [M(dmpe) (n4-butadienel21 is formed.207 At room temperature IZr(r~~-butadiene)(Bu~Cp)~l has two isomeric forms in which the diene has an s-& or s-trans conformation; low temperature photolysis o f an isomeric mixture affords the pure s-trans form.208 [Zr(n4-butadiene)Cp21 reacts with Fe(C0I5 via its s-trans form t o give (51).209 [M(n5-R5-cyclopentadienyl (nn-ring)l (M=Ti , Zr, Hf; R5-cyclopentadienyl =Cp, MeCp, Me5Cp; n=7 ring=cycloheptatrienyl ; n=8 ring=cot 1 have been studied by

A series of mixed sandwich complexes


R f l Me

( 5 4 )

‘H c-c

Me’

Me

(53)

( 5 5 ) R;C6HLMe- 4

( 5 6 ) Me

( 5 7 )

Metal-Hydrdarbon a-Complexes 321

photoelect ron spectroscopy.210 [ Z r C l (n5-C5Me4R) (n8-cot 11 (R=Me, E t ) , formed by sequent ia l a d d i t i o n o f K2fCaH81 and Li[C5Me4Rl t o ZrC14, i s a precursor t o

[ZrX(r15-C5Me4R)(n8-cot)l (X=H, a1 ky l , a r y l e thyny l ) and [ Z r ( n 3 - a l l y l l ( l -4-n4-cot.) (q5-C Me R)1; c r y s t a l s t ruc tu res of rep resen ta t i ve

complexes have been determined. 5219y212 Carbonyl exchange i n [V(CO)(n5-pentadienyl ),I and [V(CO)(n5-2,4-R2-pentadienyl )Cpl (R=H, Me)

unexpectedly occurs w i t h per f luoro-cot i n t h e presence o f two equiva lents o f PMe2R (R=Me, Ph)

affords [ N i (PMe2RI2(1 , 2 ; 5,6-1-1~-perfluoro-cot)1; an i d e n t i c a l reac t i on w i t h

a d i s s o c i a t i v e process.213 Reaction o f [ N i (n-codI2 l

ButNC i n p lace o f PMe2R g ives (52). 21 4

- E Complexes Derived f rom Acetylenes

The syntheses, reac t i ons and X-ray c r y s t a l s t ruc tu res o f [Zr(PMe3) (n 2 -cyc loa l kyne)Cp21 (cyc loa l kyne=benzyne,21 cyclohexyne216) have been

repor ted. r e a c t i o n with217 [Nb(Hl3Cp21; [TaMe(n2-RC2R){n2-C(Me)=NBut)Cpl (R=Ph, - p - t o l y l 1 undergoes thermal l y i n i t i ated coup1 i ng o f a1 kyne and i m i noacyl 1 i gands t o y i e l d (54).2'8 Treatment o f [TaC1(C0)2(dmpe)21 w i t h Mg dust i n the presence o f

[ZrCl2(Me5Cpl21 leads t o reduc t i ve coupl ing o f t he two carbonyl l igands;

subsequent a d d i t i o n o f SiMe3C1 a f f o r d s the a1 kyne complex219 CTaCl (dmpe l 2 (n2-Me3Si OC20Si Me3) 3 .

1,8-bi s-(dimethy1amino)naphthalene gives220 c r y s t a l l og raph ica l l y character ised [(W=CHPh)(Cl )2(n2-PhC2Ph)(PMe3)21. A se r ies o f complexes

[M(X),(CO)L2(q2-alkyne)1 (M=Mo, W; L=PPh3, PEt3, L2=dppe; X=Br, C1) have been syn t hesi sed and t h e s t r u c t u r e o f [Mo ( B r 1 (CO 1 ( P E t 3 1 ( n2- PhC2H 1 I determi ned

c r y s t a l l o g r a p h i c a l l y ; spectroscopic s tud ies are compatible w i t h t h e alkyne as a

fou r -e lec t ron donor.221 Analogous i o d i d e complexes are obta ined by r e a c t i o n o f P-donor l i gands w i t h [{M(u-I)I(CO)(NCMe)(n2-PhC2R)~21 (M=Mo, W; R=Me, Ph) which

f l u x i o n a l i t y o f complexes [W(SC6F5)L(r12-CF3C2CF3)Cpl [L=oxo, CO o r P-donor l i g a n d ) has been i n v e s t i g a t e d by "F n.m.r. spectroscopy.224 Grignard reagents RMgX (R=Me, CH=CH2) s e l e c t i v e l y a t tack the Mo cen t re o f [Mo { P ( OMe 1 1 ( n2- P hC P h 1 C p I ' t o y i e l d [MoR { P ( OMe 1 1 ( T-I - PhC P h 1 C p 3 ; subsequent

complexes.225 S t r u c t u r a l s tud ies on (55) suggest t h a t t he a b i l i t y o f t h e

Complex (53) i s formed by coup l i ng o f two MeCrCMe molecules

Reaction o f PhCXPh w i t h I(W=CHPh)(Cl )2(CO)(PMe3)21 i n t h e presence o f

i s a l so a precursor t o [M(I)2(CO)(NCMe)3-n(n2-PhC R) 1 ( c = l o r 2). 222,223 The 2 n

a-hydrogen e l i m i n a t i o n a f f o r d s r13-cyclopropenyl and 3 2 4 n -cyclopentadiene

keteny l l i g a n d t o ac t as a two-e lect ron donor i s i n compet fou r -e lec t ron donor capac i t y o f t h e alkyne l igand;226 (56) g i v e oxo-a1 kyne complexes [WR(O) (n2-HC2H)Cp1 (R=Me o r COMe

Reaction o f [Mn(C0I2(thf )Cpl w i t h p-diethynylbenzene complexes, [Mn(C0)2(n2-HC2C6H4C2H)Cpl and b inuc lea r

t i o n w i t h t h e r e a c t s w i t h NO t o 227

gives t h e a1 kyne

322 Organometafic Chemistry

I R " Y B '

Ph

( 5 8 )

oc 0c.J

/ CP

CP

Ph

/cp . co co

MO -

I R

(61) R = H , R ' = Ph (621 R = Me, R'= Ph (63) R = (CH2)10Me R'= Ph (65) R = R ' = M e

Me I

/C-Me c ==s c'

c p \ // \ ,co Mo-CO

CP 0 c T M 0 - \ oc

( 6 6 )

c o CP (59 ) R=SiMe,

*R' R'

\ oc

Cp- Mo-Mo-Cp

\ C / \co 8 0

(64) R = Ph , R'= H ( 6 7 ) R = H , R'= Me

Me

co co

( 6 8 )

Metal-Hydrocarbon x-Complexes 323

[{Mn(C0)2Cp12(n2,n2-HC2C6H4C2H)I; subsequent i someri sat ion, induced by PhLi , a f f o r d s t h e corresponding v iny l i dene complexes .228 Treatment o f [Re(0)3Me5Cpl w i t h PPh3 i n a f l u i d a lkyne g ives [ReO(n -alkyne)Me5Cpl complexes; prolonged

r e a c t i o n i n r e l a t i v e l y s t e r i c a l l y unhindered a1 kynes forms rhenapyran adducts exempl i f ied by c r y s t a l l o g r a p h i c a l l y characters ied (571, which i s der ived f rom

MeCXMe.229 Reactions o f 1 i thium reagents o f n i t rogen and oxygen based nuc leophi les w i t h a se r ies o f alkyne complexes [Fe(CO){P(OPh),1(n2-MeC2R)Cp3+ (R=Me, Ph, C02Me) have been inves t i ga ted and compared.230 Cyclod imer isat ion o f

PhCXH a t t h e Ru c e n t r e o f [RuBr(n-cod)Cpl a f f o r d s (58).23’ [OsI(CO)(PPh )Me Cpl w i t h AgIBF 1 i n t h e presence o f PhCZPh g i ves

[Os(CO)(PPh3:(n2~PhC2Ph)Me5Cpl+~ analogous reac t i ons w i t h te rm ina l a1 kynes y i e l d v iny l i dene complexes.

[Co2(p-Me3SiCzCSiMe3)Cp21 w i t h a c r y s t a l l og raph ica l l y determined metal -metal bond l e n g t h o f 2.18A; a d d i t i o n o f f u r t h e r [ C ~ ( n - e t h e n e ) ~ C p I y i e l d s (59) .232 ICo2(p-RC2R) (Me5Cpl21 has been obtained by r e a c t i o n o f t h e appropr ia te a1 kyne w i t h [Co( r~ -e thene)~Me~Cp l (R=SiMe3) o r w i t h amalgam reduced [{CoC1Me5Cp123 (R=Ph) ; c y c l obutadiene complexes [Co(n4-R I 4cbd )Me5Cpl (R’=C02Me, S i Me3) have

a l so been iso la ted.233 Reaction o f trans-[RhCl (PPr~),(n2-PhC2R)1 (R=H, Ph) w i t h NaCp g ives [Rh( PPr i ) (n2-PhC2R)Cpl; subsequent treatment w i t h CF3C02H af fords234

a lkenyl complexes [Rh(nl -CPh=CHR){OC(O)CF,}(PPr~)CpI. Reaction o f [Rh(PPrS)(n2-PhC2H)Cpl w i t h [Fe2(C0)91 g ives (60) and v iny l i dene bridged235 [Rh(PPri)Cp(u-CO) (p-C=CHPh)Fe(C0)31. B is-a lkyne complexes

- cis-[M(C6F5),(n2-PhC2Ph)l (M=Pd,Pt) have been prepared and the p la t inum complex

cha rac te r i sed c r y s t a l 1 ographica l ly;236 bul k reduc t i ve e l e c t r o l y s i s o f

- ~ i s - [ P t C l ~ ( P P h ~ ) ~ l forms 14-e lect ron [Pt(PPh3l21 which i s trapped by a l k y n e ~ ~ ~ ’

t o g i v e [Pt (PPh3)2(n2-a lkyne) l .

2

Treatment o f

35

Reaction o f [Co( r~ -e thene)~Cp l w i t h Me3SiCXSiMe3 a f f o r d s alkyne br idged

- F Polynucl ear Complexes

1 Bimetal 1 i c Complexes

t reatment o f [Mo , (CO)~C~~I w i t h L i [C2Phl, reac ts w i t h e l e c t r o p h i l e s t o g i v e complexes (61 1, (62) and (63) which e x h i b i t a b r i d g i n g n1,n2-(4e)-vinyl idene l igand, confirmed c r y s t a l l o g r a p h i c a l l y f o r (63 ) . Rearrangement o f (61 1 a f f o r d s [ M O , ( C O ) ~ ( ~ - P ~ C ~ H ) C P ~ I and thermolys is o f (62) g ives a l l y 1 idene br idged (64 ) . 238

Var iab le temperature ’ H n.m.r. s tud ies on (65) and i t s tungsten analogue reveal t h a t s i t e exchange o f t h e b r i d g i n g n1,n2-(4e) v iny l i dene l i g a n d occurs 5 a TI’ ,n1-(2e) v iny l i dene b r idged in termediate; a l l e n y l i d e n e br idged (66) , synthesised by p ro tona t ion o f t h e anion formed from r e a c t i o n o f [Mo2(C0I4Cp21 w i t h Li[CX-C(Me)=CH21, has been inves t i ga ted f o r a l l e n y l i d e n e s i t e exchange and

character ised crystallographically.239 A l l y l i d e n e complex (671, synthesised

- The a c e t y l i d e br idged complex L i [ M o ~ ( C O ) ~ ( U - ~ ~ ,n2-CXPh)Cp21, formed by

324

Me


Ph

cp\

/ oc

Mo Mo’ co \ / \‘co

C CP 0

( 6 9 )

R’

RO ,OR

PY’I\ /w\OR

R O L W ’ -PY

0 0 R R

(73) R = CH2But R’= H or Me

‘C./

OC \MO- 1 / kM0,CP

cp’ \ f ‘co

0 / n c C H H

P

R ’

‘& ,OR w-L

RO’ \ / ‘OR 0

Ro\ / RO-W

R

(74) R = CH2But R’= Et or Ph , L : py ( 7 5 ) R = Bu‘ I R‘= M e L = CO


f rom [Mo (CO)4Cp21 and 3,3-dimethylcycl opropene, undergoes thermal rearrangement

t o y i e l d*40 a m ix tu re o f [Mo2(C0 )4(u-PriCzH )Cp21, [Mo2(CO),(~-CH2=CH-C(Me)=CH2)Cp21 and (68 ) . Reactions o f (67) w i t h 1 ,Z-dienes,

lY3 -d ienes and alkynes a re postu la ted t o proceed v i a v iny lcarbene br idged (69) ; a wide v a r i e t y o f c r y s t a l l o g r a p h i c a l l y character ised products are formed.241

[Mo2(C0 3( PPh3 1 (p-HC2H )Cp,l , t h e i n i t i a1 product o f r e a c t i o n between [ M o ~ ( C O ) ~ C P ~ I and PPh3, isomerises t o (70) i n r e f l u x i n g to luene via phosphorus-carbon bond cleavage; i n t h e PPhzH analogue P-H bond cleavage i s

prefer red.242 One-electron reduct ion of [Mo(NCMe) (n2-MeC2Me)2(n-indenyl)1 [BF41

a f f o r d s t h e c r y s t a l l o g r a p h i c a l l y character ised ' f l y ove r ' complex (71 1; subsequent r e a c t i o n w i t h CO g ives t h e adduct [Mo2{u-(q1 ,n3:~3,~1-C6Me6)l(CO)2(n-indenyl ),I i n which t h e Mo-Mo bond order i s

un i ty .243 Photo lys is o f [Moz(C0)6(~5y~5-fulvalene~l w i t h a1 kynes g ives

[Mo2(C0 14( u-RC2R 1 (n5,n5-ful va l ene 11 and [ M O ~ ( C O ) ~ ( ~ ~ - R C ~ R 1 (u-RC2R 1 (n5,n5-ful va l ene) I (R=Ph, C02Me). 244 Heats o f

r e a c t i o n o f alkynes w i t h [Mo2(CO),(n5-ring),1 have been used t o est imate t h e s t rength o f t he Mo-Mo t r i p l e bond.245

o f [Co2(C0),(~-CF3C2CF3) 1 w i t h N ~ [ M o ( C O ) ~ C ~ I af fords246 heteronuclear,

a1 kyne-bridged [ C O ( C O ) ~ ( ~ - C F ~ C ~ C F ~ ) M O ( C O ) ~ C ~ I ; and complexes (72) are formed f rom Na[Re(CO),-] and [Mo(CO) (PR3) (Q'-R'C~R' )Cpl [BF41 (R=al k y l , ary l , R'=Me,

Ph).247

depending upon s t e r i c f a c t o r s associated w i t h t h e alkyne s u b ~ t i t u e n t ; ~ ~ ~ t h e e q u i l i b r i u m [W2(OR)6(py)n(u-CzR'z)l +2[WXR'(OR)31 t n py (n=1,2) has been examined f o r complexes (73) and (74).249

induced a l ky l i dyne -a l ky l i dyne coupl ing of [ W E C M ~ ( O B U ~ ) ~ I ; by con t ras t analogous

treatment of [WXNMe2(py)2(0Pri ),I a f f o r d s t h e terminal alkyne complex (76) .250 A t -20°C [W2(NHMe2!2(0Pr' ),I reac ts w i t h E t C X E t t o g i v e [{WXEt(NHMez)(OPr' )2(u-OPr' )Iz] bu t a t room temperature a m ix tu re o f products,

i n c l u d i n g (77) and (781, i s formed.251

[ t W C l (NMe2) (py))2(u-NMe2)2(u-al kynel l , synthesised by t reatment o f [W2C12(NMe2)41 w i t h alkynes i n t h e presence o f py r id ine , undergo thermolys is t o

y i e l d e i t h e r [{WCl(py)12(u-C1 )(u-NMe2)(u-alkyne)l o r [{W(Cl ),(py)I,(u-NMe,),(u-al k y n e l l depending upon f a c t o r s associated w i t h t h e alkyne subs t i t uen t . (alkyne=MeCECMe) revea ls t w i s t i n g o f t he alkyne w i t h respect t o t h e W-W axis252

and extended Hl/ckel c a l c u l a t i o n s have been c a r r i e d ou t t o p rov ide a r a t i ~ n a l i s a t i o n . ~ ~ ~ Reaction o f [W2C13(NMe2)3(PMe2R)21 (R=Me, Ph) w i t h HCXH af fords adducts [ { W C l (NMe2) ( PMe2R) 12(u-C1 ) (u-NMe2) (v-HC2H)I which isomeri se t o v i n y l br idged (79) i n t ramo lecu la r H atom t r a n s f e r f rom NMe2 t o e t h ~ n e . ' ~ ~

Treatment o f a1 ky l i dyne br idged [MO(Co),Cp{u-C(C6H4Me-4) lFe(C0)41 wi th excess

( r i n g = Cp, Me5Cp, i ndeny l ) Treatment

Alkynes reac t w i t h [W2(OCH2But)6(py)21 t o g i v e 1 : l adducts (73) o r (74)

Complex (75) i s formed249 by CO

Alkyne adducts

Crys ta l l og raph ic cha rac te r i sa t i on o f t h e l a t t e r complex


O L R

( 7 6 ) R=Pr ‘

E t

RO R

Et (77) R = Pr’

R H2C = CH

Me,N /p2 \ \ / \ L-w-w- / \ / ‘c,

N= CH2 RO CL /

Me / \

RO OR

(78) X - C E t R = Pr‘

H ‘C - - CHR

H2 R = C6HLMe- 4

(80) M = M o , L - C p (81) M = W L=Mc,Cp

( 7 9 ) L = PMe2Ph or PMe,

CP \Fe - Fe

oc’ \/ ‘co 0

(82) R = H ( 8 3 ) R=C02Et


diazomethane g ives (80);255 t h e r e l a t e d tungsten complex (81) i s formed by an

analogous r e a c t i o n w i th256 [W(CO) 2Me5Cp{u-C (C6H4Me-4) )Fe(CO ),I .

CH’) have been i n v e s t i g a t e d by Fenske-Hall molecular o r b i t a l c a l c u l a t i o n s and c o r r e l ated w i t h t h e r e a c t i v i t y o f these complexes towards a1 kynes o r a1 kenes . 257 A se r ies o f a lkeny l b r i dged complexes [{Fe(CO)Cp)2(u-CO) (u-T-I’ ,n2-CH=CRR’ 11’ (R,R’=H o r a l k y l 1 have been prepared by r e a c t i o n o f [{Fe(CO)Cp) (u-CO)(u-CH)I+

w i t h alkenes such as ~ i n y l a c e t a t e , ~ ~ ~ b ~ t e n e , ~ ~ ’ isobutylene,26d and 1 -methylcyclohexene.261 Reaction o f a1 kenyl br idged

[ {Fe(CO)Cp}2(~-CO)(u-~1 ,n2-CH=CHR)I [PF61 (R=H, Prn) w i t h CH3CN af fords262

mononuclear complexes [ F ~ ( I - I ’ - C H = C H R ) ( C O ) ~ C ~ I . Low temperature pho to l ys i s o f

complexes (82)263 and (83)264 r e s u l t s i n cyc lopropy l idene r i n g opening and format ion o f a1 lene-br idged [{Fe(CO)Cp)2(~-n2,n2-H2C=C=CHR)l. Treatment o f [{Fe(NO)Cp}2(p-CH) 1 w i t h [Ph3CI[PF61 a t -78°C g ives [ { F e C p ( ~ - N 0 ) ) ~ 1 and

[iFe(NO)Cp12(U-I-11 ,z2-CH=CH2)1 [PF61; t h e product m ix tu re f rom r e a c t i o n a t room temperature i nc 1 udes265 methyl i dyne-bri dged [ { Fe ( U- NO )Cp l2 ( U-CH 1 3 [ PF61 . Formation o f [Fe2(C0)6(U-C1 1 (p-nl ,n2-CPh=CHPh)l f rom PPh4[Fe2(C0)6(u-CO) (u-rl’ ,n2-CPh=CHPh)l and [Me3Ol [SbCl61 i s thought t o proceed v i a methy lat ion o f t h e b r i d g i n g C O l igand;266 PPh 4 2 [Fe (CO)6(~-CO)(u-n1 ,r~~-cH=CHPhll reac ts w i t h C O ~ ( C O ) ~ t o g i v e heteronuclear

a1 kenyl bridged267 [Fe(CO)4(u-n1yn2-CH=CHPh)Co(C0)31. Replacement o f t he b r i d g i n g CO l i g a n d i n Et3NH[Fe2(C016(u-CO) (U-SEt j I by r e a c t i o n w i t h CH2=CHHgBr

o r ( PhCXI2Hg affords,268 respec t i ve l y [Fe2 (C0)6 (~ -SEt ) ( u - n l ,n2-CH=CH2)l and [Fe2(C0)6(U-SEt 1 (p-nl , ~ I ~ - C X H ) ~ . Photoelectron spect ra o f

[Fe2(C0)6(u-ButC2But)l are repor ted and assigned on t h e bas is o f ab i n i t i o s e l f -cons is tent f i e l d and con f igu ra t i ona l i n t e r a c t i o n c a l c u l a t i o n s c a r r i e d

out269 on t he model system [Fe2(C0I6(~-HC2H)I . Oxidat ion o f v i n y l i d e n e br idged [{Ru(CO)M~,C~}~(LI-CO) (u-C=CH2)1 w i t h two

equiva lents o f Ag[BF41 i s thought t o r e s u l t i n proton e j e c t i o n and format ion o f

[{Ru(CO)Me5Cp12(u-CO){u-T-11 ,n2-CXH)1 [BF41; subsequent chromatography on alumina y i e l d s the c r y s t a l l o g r a p h i c a l l y character ised keteny l br idged complex270

[{Ru(CO)Me5Cp12{~-C(0)-CH2)1. [Ru2(C0)6(u-PPh2) (p-n’ ,n2-CXPh)l a f f o r d s a l l e n y l br idged complexes o f s t r u c t u r e (841, confirmed c r y s t a l l o g r a p h i c a l l y f o r t h e phenyl d e r i ~ a t i v e . ~ ~ ’

l i gands L add t o t h e Ru(C01, cen t re o f t h e ~ - ~ ~ , n ~ - d i p h e n y l f u l v e n e complex (85) t o g i v e [ R U ( C O ) ~ L ( P - ~ ’ ,~5-6,6-diphenylfulvene)l complexes. 272

has been obta ined f rom low temperature x - ray and neutron data and f rom t h e o r e t i c a l wave function^;^^^ t w i s t i n g o f t h e a1 kyne w i t h respect t o t h e Co-Co ax i s i n [ C O ~ ( C O ) ~ ( U - H C ~ H ) I has a l so been s tud ied t h e ~ r e t i c a l l y . ~ ~ ~ Rad io l ys i s o f C O ~ ( C O ) ~ i n benzene affords275 low y i e l d s o f [Co2(C0)6(~-cyclohexyne)l and

The e l e c t r o n i c s t r u c t u r e s of [{Fe(CO)Cp)2(~-CO) ( u - L ) ~ (L=CO, CH2, C=CH2,

Reaction o f diazomethanes N2CR2 w i t h

Lewis-base

The e l e c t r o n deformation dens i t y d i s t r i b u t i o n i n [Co2(C0),(u-ButC2But)1


R I

(CO I3R u - \ P /Ru(c0'3

Ph2

(84) R = H , Me or P h

F5v , SF5

(CO),

(CO),Ru-Ru (CO),

(85)

Me Ph


Cp F3cmc:co Rh RG Cp

1 co

( 9 0 )

l+ -----\ I

I I (CO),Fe -Rh(nbd)

( 9 3 )

‘R h-Fe (CO), L’

(91) L = co (92) L = phosphinc

Cp Rh-RhCp

(94 1

( 9 5 ) (C01,

(96) M = R u , O s

3 30 Organometallic Chemistry

reac t i on

(86) f o r ICo,(CO)

o f C O ~ ( C O ) ~ w i t h HCrCSF5 g ives a se r ies o f complexes

n=3.

7-n(HC2SF5)n] (;=1,2 o r 31, character ised c r y s t a l l o g r a p h i c a l 1y276 as Alkyne-bridged [CoMn(C0),(p-PhC3Me)l r e a c t s w i t h PhCECMe t o g i v e

the heteronuclear f e r r o l e complex (87) .z77

dependent upon t h e a1 kyne subs t i t uen t ; one-e lect ron ox ida t i on o f t h e But d e r i v a t i v e g ives a s tab le r a d i c a l monocation which has been inves t i ga ted by e.s.r. spectroscopy.278 Ethene and i t s s u b s t i t u t e d d e r i v a t i v e s r e a c t w i t h

[Rh2Cp2(p-CO)(p-CF3C2CF3)1 t o g i v e b i s a1 kenyl -br idged complexes [Rh2Cp2{p-n1 , T - I ~ - C ( C F ~ ) = C H ( C F ~ ) } ( ~ - T - I ~ , ~ ' - C R = C H R ' 11; w i t h alkynes R C X R ' , a v a r i e t y o f products (881, (89) or (90) are formed depending upon the alkyne

substi tuents.280

phosphines t o g i v e (92) o r carbonyl br idged [Fe(CO 1 2(p-C0 1 (u-n4,n3-C7H7 )Rh (phosphi ne 1 21 ; t h e 1 a t t e r complex, cha rac te r i sed c r y s t a l l og raph ica l l y f o r (phosphineI2=dppe, exhi b i t s reversed

meta l -cyc loheptat r ieny l bonding modes by comparison w i t h (91 1 and (92 ) . Carbonyl scrambling i n these complexes has been examined by low temperature 13C

n.m.r. spectroscopy.281

demonstrated by the synthes is o f b inuc lea r complexes such as (93) and (94) .

[Mn2(CO) (p-q2,r12-allene)l complexes together w i t h o the r mono- and b inuc lea r products. 8283y284 The major products o f i r r a d i a t i o n o f [Re2(CO)lol w i t h ethene

o r 2-methyl-l,3-butadiene are [Re2(C0)8(p-H) (p-nl , n2 -o le f i ny l 11 and [Re3(C0Il3(p-q1 ,q2 -o le f i ny l 11 complexes.285 The r a d i c a l monocation formed by

one-electron ox ida t i on o f [Pd2(Ph5Cp),(p-PhC2Ph)l reac ts w i t h dppe and dienes t o g i ve [PdL2(Ph5Cp)lt (L2=dppe, nbd, cod, c o t ) .286 Octadienyl br idged (95) and

- t The e lec t rochemis t r y o f [Rh2Cp2(p-CO)(p-RC2R)1 (R=Bu o r CF3) i s s t rong ly

279

The cyc lohep ta t r i eny l br idged complex (91 1 reac ts w i t h

The v e r s a t i l i t y o f c o t as a b r i d g i n g l i g a n d has been 282

I r r a d i a t i o n o f [Mn2(CO)101 w i t h CH2=C=CR2 (R=H o r Me) a f f o r d s

re1 ated complexes have been synthesi sed and appl i e d i n t h e t e l omeri s a t i o n o f

butadi ene. 287

- 2 Po lymeta l l i c Complexes

(96) has been s tud ied by 'H and v a r i a b l e temperature 13C nmr, by CNDO

t h e o r e t i c a l techniques and, i n the case of [ t O s ( C O ) 3 ) 3 ( ~ - H ) 2 ( ~ 3 - M e C 2 M e ) l , by use o f X-ray c r y s t a l lography.288 Two-electron reduc t i on o f t he perpendicu lar p3- i2-a lkyne c l u s t e r (97) occurs i n two almost r e v e r s i b l e steps t o y i e l d the corresponding d ian ion [{Fe(CO)3)3(u3-EtC2Et)12- i n which the alkyne i s be l ieved t o be reo r ien ta ted t o a p a r a l l e l p3-bonding mode. By con t ras t reduc t i on o f (96) (R=Et), (98) or [ F ~ C O ~ ( C O ) ~ ( ~ ~ - E ~ C E t ) l i s an i r r e v e r s i b l e process, probably associated w i t h c l u s t e r b r e a k d 0 ~ n . l ~ ~ A k i n e t i c study has been made o f t h e h igh temperature r e a c t i o n between O S ~ ( C O ) , ~ and PhC-CPh under var ious p a r t i a l pressures o f CO and t h e mechanisms involved i n format ion o f products (99), (100)

The para1 1 e l p3-q2-al kyne-cl u s t e r i n t e r a c t i o n i n compl exes o f s t r u c t u r e


Ph \ /’”

( 9 7 )

Ph

(100)

1-

R

(CO ),Fe -

(102) R = H , X = C o (108) R = P h , X = C O

(109) R = Ph, X = Fc(C01,

R I

(98 ) R = Et (99) R = Ph

(101)

L 0


( 1 0 4 ) X = c o ( 1 0 5 ) X = H -

Ph

(107)

(CO

(110)

R R

1-

( 1 1 1 ) R = Toly l (112) R =Toly I

Metal-Hydrocarbon z-Complexes

R‘

333

R

(113) R =Tolyl

p)=( Ph

H OMe ‘c=

I ‘c=c

I p c

/ Ph

(11 7 )

R

P R

Ph


and (101 1, i n ~ e s t i g a t e d . ~ ” A t room temperature [PPh41 [Fe3(CO)lo(~2-H)(~2-CO)l reac ts w i t h ethyne t o g i v e a m ix tu re o f (102) and (103) (R=H).

a1 ky l i dyne complex (103) (R=H) w i t h [Ph3CI+ affords v iny l idene-br idged (104) (R=H); t h e r e l a t e d complex (105) (R=H) r e s u l t s f rom thermolys is o f (103) (R=H)

i n r e f l u x i n g acetone. Treatment o f (103) (R=H) w i t h H+ o r [Et301[BF41 gives291

respec t i ve l y neu t ra l , a1 k y l idyne-bridged c l u s t e r s

[{Fe(CO ),I3( u2-H 1 ( u3-C0 (p3-CMe) I and [{Fe(CO) 313(v3-CMe) (u3-COEt) 1. reac t i on of s u b s t i t u t e d alkynes RCXH [R=Ph, Prn, C(O)Me, C(0)OMel w i t h

[PPh41[Fe3(CO)lo(p2-H)(~2-CO)~ gives (103) a t room temperature o r (105) i n

r e f l u x i n g acetone. are converted t o acety l i de-b r i dged ( 106). 292 Three separate syntheses o f (1 07 1, - v i a treatment o f any one o f t h e anion ic complexes (1081, (109) o r (110) w i t h

[Ph3CI+, have been reported.293 Terminal alkynes H C X R ’ (R’=Me, Ph) i n s e r t i n t o

the Fe-P bond of t e t ranuc lea r (111) t o g i ve (1121, c r y s t a l l o g r a p h i c a l l y 294 charactersed f o r R’=Ph; subsequent r e a c t i o n w i t h CO a f f o r d s t r i n u c l e a r (113).

Photochemical a d d i t i o n o f alkynes R ’ C X R ’ (R’=Me, Ph) t o [{Fe(C0)3}3(u3-PR)21

(R=Ph, C6H40Me-4) g i ves complexes (114) which, upon thermolysis, y i e l d (115) o r

a l t e r n a t i v e l y 2 9 5 re fo rm [{Fe(C0)3)3(u3-PR)21. Reaction o f PhCXPh w i t h

n i t rene-br idged [{RU(CO)~),(~,-CO)(LI~-NP~)I gives me ta l l apy r ro l i done complex

(116) - coup l i ng o f t h e alkyne w i t h b r i d g i n g CO and n i t r e n e l igands.

Reaction o f alkyne-bridged [ O S ~ ( C O ) ~ ~ (u4-S)(u4-HC2C02Me)J w i t h PhCXH o r a1 lene

af fords, respec t i ve l y , (117) and (118) a C - C bond coup l i ng o f PhCECH o r a l l ene

w i t h coord inated HCX,C02Me.297 The f u l l c r y s t a l lographic cha rac te r i sa t i on o f

(119) and (1201, synthesised by treatment o f I R U ~ ( C O ) ~ ~ I w i t h MeCXCH2NMe2, has

-een reported.298 Reaction of MeCXNEt2 w i t h [Fe3(C0)121 affords two b inuc lea r

and two t r i n u c l e a r products; c rys ta l l og raph ic cha rac te r i sa t i on o f t he t r i n u c l e a r

species reveals , i n each case, C-C bond coupl ing between two MeCXNEt2

molecules .

78-e lect ron bis-phosphido complex (122);300 (121

diphenyldiazomethane t o g i v e (123) i n which t h e N2CPh2 group ac ts as a 6 e lec t ron ~ ~ - 1 i g a n d . ~ ” Oxidat ive a d d i t i o n o f [Au(CXPh)LI (L=PPh3, PMe2Ph) t o

[Os3 (CO l1 O(MeCN) 21 a f f o r d s phenyl e thyny l -br idged complexes (1 24) which undergo

thermal decarbonylat ion t o complexes (125).302

t o the b r i d g i n g ethyny l l i g a n d o f (126) y i e l d s (127) and (96) (M=Os, R=H,

R’=OEt); r e l a t e d add i t i ons o f NH3 and p y r i d i n e are a l so repor ted.

[ { O s ( C O ) , ~ 3 ( ~ 2 - H ) 2 ( v , - C ~ C H ) l f , t h e edge protonated d e r i v a t i v e o f (1261, reac ts

w i t h water t o form [{O~(CO),(LI~-H)}~(~,-CH)I and [{Os(CO) (11 - H I 1 (LI -CCHO)l

nucleophi l i c a t tack a t a- and 8-ethynyl carbons r e s p e c t i ~ ~ l y ? ~ ~ ~ 3Hyd3rogenation

of [ ~ O ~ ( C o ) ~ } ~ ( u , - c P h ) (u3-COMe)] induces a l ky l i dyne -a l ky l i dyne caupl ing and

formation o f (96) (M=Os, R=OMe, R’=Ph); a l t e r n a t i v e l y reduc t i on and subsequent

Reaction o f

S i m i 1 a r l y ,

I n r e f l u x i n g 2-methoxyethanol complexes (105) (R=Ph, Prn)

296

299

Add i t i on o f diphenylphosphine t o t h e 74-e lect ron c l u s t e r (121) g ives the reac ts w i t h

Nuc leoph i l i c a d d i t i o n o f ethanol


( C

H

( CO),

A

(121) X = Ru(C01, (123) X N2CPh2

Ph

(122)

(CO),

(125) R=Ph , X = A u ( L )

(126) R = H , X = H


304 pro tona t i on y i e l d s (1 26 1 (R=Ph 1. The s o l u t i o n s t r u c t u r e and dynamics of a1 kenyl -br idged complexes (128) has

been inves t i ga ted by ' H and 13C n.m.r. spectroscopy.305 Phenyl v i n y l su lph ide i n s e r t s i n t o an 0s-H bond o f [Os3(C0)10(~2-H)21 t o g i v e t h e two diastereomers o f

(129) as major products; by con t ras t C-S bond cleavage occurs on r e a c t i o n w i t h

[Os,(CO), (NCMe)21 t o g i v e c r y s t a l 1 ographical l y cha rac te r i sed ( 1 30). 306 Reaction o f [Os3(C0)10(~2-H)21 w i t h v i n y l acetate g ives (131 1 as t h e major product together w i t h small q u a n t i t i e s o f (128) (R=H).307 The b r i d g i n g ketene

l i g a n d i n c l u s t e r (132) i s converted t o an enolate l i g a n d by r e a c t i o n w i t h 308 nucleophi les o r t o an acy l o r v i n y l l i g a n d r e a c t i o n w i t h e lec t roph i l es .

C r y s t a l l o g r a p h i c a l l y character ised (133) has been i s01 ated as an in termediate

from the [CpNiOs ( U ~ - H ) ~ ( C O ) ~ I cata lysed homogeneous hydrogenation o f penta- lY3-d iene.

s t r u c t u r e (134); i n t h e r e l a t e d [Ir (CO)10(s4-diene)l complexes the diene i s

o r Ph) reac t w i t h [NOl[BF41 t o g i ve a l k a n e n i t r i l e ox ide c l u s t e r s (135); attempts

t o deprotonate (135) (R1=But, R2=H o r But) r e s u l t i n format ion o f (136) v> a1 kyl idyne-a1 ky l i dyne coup l i ng and simultaneous NO de inse r t i one311

[{CoCp} 3 2 (LI -H) ( ~ ~ - C H ) ~ l + t h e edge-protonated d e r i v a t i v e o f [ { C O C ~ I ~ ( ~ ~ - C H ) ~ I , reac ts w i t h CO a t 23°C t o g i v e (137); f u r t h e r ca rbony la t i on a t 70°C y i e l d s (138) apparent ly v i a methyl idyne-methyl idyne coupl ing and simultaneous CO d e i n s e r t i o n T 2 Var iab le temperature 3C nmr s tud ies and extended H k k e l

c a l c u l a t i o n s suggest a C, geometry f o r k e t e n ~ l i d e n e - b r i d g e d ~ ' ~ complexes (139), [Co3(C0 18( PPh3) (p3-C=C0) It and [ C ~ M O C O ~ ( C O ) ~ ( I J ~ - C = C O ) J '. Reaction o f C O ~ ( C O l8 w i t h [Fe(n'-C?CPh) (CO)2Cpl a f fords314 c r y s t a l l o g r a p h i c a l l y characterised, alkyne

br idged [ C O ~ ( C O ) ~ { ~ - P ~ C ~ F ~ ( C O ) ~ C ~ ~ I ; t he l a t t e r complex and i t s Ru d e r i v a t i v e

undergo a non-dest ruct ive r e a c t i o n w i t h O2 t o form a l ky l i dyne -b r idged [CpM(CO),Co,(CO),(p,-CPh)l (M=Fe, Ru) .315 The i n t e r a c t i o n o f ethyne w i t h a P t (1 11 ) sur face has been model l e d by r e a c t i o n o f ethyne w i t h [ P t ( p -H)(p-dppm)31t forming (140) via an in termediate q2-alkyne complex. 31 6

(M=Fe, Ru, 0s ) have been synthesised and character ised c r y s t a l l o g r a p h i c a l l y . t he i r o n complex (141 1 t h e alkyne i s o r i e n t a t e d p a r a l l e l t o t h e Ni-Co edge but i n [CpNiCoM(CO) (u3-PhC2Ph)l (M=Ru, 0s) t he alkyne o r i e n t a t i o n i s p a r a l l e l t o the N i - M

( 1 4 3 ) m a l k y l i d y n e (144) (R=H, But) has been reported318 and the d ias te reose lec t i ve synthes is o f (143) (R=Me, But) (which conta ins two asymmetric cen t res ) and o f s t r u c t u r a l l y analogous complexes, has been examined.319

Reaction of [PPh41 [Fe2(CO)6(~-COI (p-s' ,t12-CH=CH2)] w i t h [{Rh(C0)2C1)2] a f f o r d s

[pph4] [~e3Rhp(CO

j o g

Reaction o f [NEt41[Ir4(CO)11Brl w i t h monoalkenes a f f o r d s c l u s t e r s o f

r) 4 -bonded t o a s i n g l e Ir centre.3104 [{CoCpI3(p3-CR 1 )(u3-CR 2 11 (R1,R2=H, a l k y l

3 3 A se r ies o f h e t e r o t r i m e t a l l i c alkyne c l u s t e r s [ C ~ N ~ C O M ( C O ) ~ ( I J ~ - R C ~ R ) I

I n

The r e v e r s i b l e t ransformat ion alkyne (142) 4 v iny l i dene

IJ-CO) 3( I J ~ - ~ ~ - M ~ C = C = C H ~ ) ] i n which the 3-methyl -3-a1 1 eny l


(127) (128) R = H Ph But, Si Me,

(129) R R'= M e , H (130)

Me I

0 /-0 I 1-

H,C - (131)


( COI, I r

C P

( 1 3 3 )

1’ ‘ C P

(135) X = NO (137) X = C H ,

1 2 R = O H , R = H

H /

H ‘ C C C

bH- - c o c p

0’ ?‘c\( I-‘ COCP 7 c p c o -

1’

(136)

1’

l+

(130) (139)

Me tal-Hydrocarbon I[- Complexes 339

L

( 140 )

H R /

Cp Mo (CO),

l+

2

Et Et ‘C-C /

/H

H2CR I


l i g a n d i s u4-bonded t o a RhFe4 u n i t which c o n s t i t u t e s t h e base o f a square

pyramidal arrangement o f t h e f i v e metal atoms. 320

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S.H. Han, G.L. Geoffroy, and A.L. Rheingold, Organometallics, 1986, 5 , 2561. R.D. Adams and S. Wang, Organometallics, 1986, 5, 1274. S. Aime, D. Osella, A.J. Deeming, A.J. Arce, M.B. Hursthouse, and H.M. Dawes, J. Chem. SOC., Dalton Trans., 1986, 1459. E. Cabrera, J.-C. Daran. Y. Jeannin, and 0. Kristiansson.

1986, 307, 237.

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307.

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- -

14 n-Cyclopentadienyl, n-Arene, and Related Complexes*

1 Introduction BY A. H. WRIGHT

The rapid development of cyclopentadienyl chemistry of the early transition metals, lanthanides and actinides is a noteable feature of the 1986 literature. In arene chemistry, further reports of uranium arene complexes and the report of the first lanthanide arene complex confirm that these complexes are isolated examples of an emerging class.

Reviews for the year have included a discussion of the use of [CpFe(arene) 1' complexes as electron reservoirs' and a description of these complexes as photopolymerisation initiators.2 The utilisation of [2nl cyclophane transition metal complexes to form one-dimensional n-electron delocalised polymers has also been e~amined.~ The place of Cp*Re03 chemistry in the burgeoning field of high oxidation state half sandwich complex chemistry has been covered. Applications to organic chemistry have been described, including an examination of the stereochemistry of reactions involving metallocenes5 and applications involving the CpFe(C0)z moiety.6 A review of the biochemical applications of metallocenes includes their use as antiturnour agents7 and the preparation of steroidal hormones using (arene)Cr (CO) 3 has been covered. The importance of cyclopentadienyl as a spectator ligand is emphasised in reviews of electron transfer reactions and transient radicals in organometallic chemistry9 and the chemistry of molybdenum alkyne complexes. lo

Emphasis in this report is placed on chemistry that involves the aromatic ligand directly. Reactions that involve replacement or elaboration of other ligands present are generally not included. Similarly, a very selective approach is taken to complexes containing metal-metal bonds, or hydrocarbyl ligands (see Chapters 9-13).

* Throughout this review the abbreviations Cp, Cp', Cp*, Bz and hmb explicity ( n5-C5Me5), ( n6-C6H6) and (n6-cg~e6) respectively.

denote (r15-C5H5) I (n5-C5H4Me) I



2 Monocyclopentadienyl Complexes

2.1 Titanium, Zirconium and Hafnium: A new type of macrocyclic sandwich complex (1) has been isolated from the reaction of the parent macrocyclic complex with NaCp. The same product has been characterised from the reaction when Ti( tmtaa)C1211 or Ti( tmtaa)C112 is used as the substrate complex. The analagous vanadium complex CpV(tmtaa) has been prepared and demonstrated t o contain 2 unpaired electrons compared with the single unpaired electron in the titanium complex.12 A

more conventional complex CpTi ( rl2-O2C6H4)C1 is generated from the reaction of Ti ( o ~ c G H ~ ) c ~ ~ with T1Cp.13

used to generate the first carbonylate anions of Ti and Zr.14 The Cp derivatives have also been reported . A range of mixed polyolefinic zirconium sandwich complexes (2) have been made by sequential addition of Kz(C8H8) and substituted Li(CsMe4R) to ZrCl4. Reactions of the remaining halide on the metal have also been reported.15 The transformation of Cp*TiC13 into Cp*Ti (CH2Ph) 3 has been described.16 The hydrolysis of these trialkyl derivatives can lead to polymetallic complexes such as Cp"3Ti3Me3 (p-0) 3 leads to cleavage of one of the Cp rings and formation of Cp2Zr2 ( p-OH) 2 (H20) 6. l8 The addition of cyclopentadienyl metallate fragments to heteropolytungstates silicates21 for applications such as electron microscopy and supported catalysis have also been reported.

Reductive carbonylation of Cp*MC13 at low tempera tures has been

while in the case of Cp~ZrCl2 hydrolysis

* O and

2.2 Vanadium, Niobium and Tantalum: A mild reagent for introducing substituted cyclopentadienyl ligands, (CsH4R)SnBu3, has been used to generate complexes such as (c~HdR)NbC14.~~ The unususal bridged complex (3) results from the substitution of indene from CpNb( ind) by ethylene. 23

The generation of new paramagnetic complexes and the study of their reaction chemistry has received considerable attention. The reduction of CpVX2(PR3)2 complexes with A1 or Zn gives the paramagnetic species [CpVX2(PR3)12 and simple substitution chemistry has been investigated.24 The Cp" complexes of Ta have allowed the investigation of some early transition metal-silicon bond chemistry including the complex Cp*Ta( SiMe3)Cl~ and the novel adduct Cp*Ta (C (0) (SiMe3) ( py ) )C13. 25

a-Cyclopentadienyl, a-Arene, and Related Complexes 353

T i

M Ph

n

(3) Ph

(4 1

r 1-

L J


2.3 Chromium, Molybdenum and Tungsten: The cyclopentadienyl chemistry of these three elements continues to be dominated by chemistry in which the Cp remains a spectator ligand. However a number of reactions involving the introduction of Cp rings include the photochemical reaction of W(C2Ph)z(S2CNMe2)2 with phenylacetylene to give (4). 26

attack by cyclopentadienyl on acetonitrile followed by hydrolysis of the intermediate. 27 Other syntheses include the tied complex ( C O ) ~ W ( C S H ~ ) S ~ M ~ ~ ( C ~ H ~ ) W ( C ~ ) ~ ~ ~ and new types of fulvalene complex such as (6) 29 and the anion [ (CC,H~CHO)C~(CO)~]-.~* The preparation and structure of the bisallyl complex CpCr ( q3-C3H5) 2 has been described. 31

is one of a number of reports of related complexes. A detailed study of the electrochemically generated CpMo(C0)3 and tungsten analogue has been described33 and interest in the parent dinuclear species has included an electrochemical study of the related 10-electron tied fulvalene complexes ( C ~ O H ~ ) M ~ ( C O ) ~ (M=Cr, Mo and W). This study has been extended to the Ru analogue.34 A kinetic study of the reactions of the paramagnetic complex CpW(CO)3 led to the conclusion that substitution reactions are associative .35

The formation of (5) has been reported to involve nucleophilic

The structure of the paramagnetic complex CpCr (CO) 2PPh332

Three reports of photochemical studies of CpMR(CO)3 complexes have appeared. These include the reaction of CpMoMe(C0)3 with ~yclopentadiene~~ while in a flash photolysis study of CpWR(CO)3 (R=Me or Et) both ci and B-elimination processes have been observed.37 In the third report the formation of [PPh3Mel[CpW(C0)3] from CpWMe(C0)3 was proposed to proceed via a radical mechanism. 38

The unusual MoIV complex CpMo(q5-C3H5)Br2(C0) has been characterised following oxidation of the parent dicarbonyl complex. 39 Matrix photolysis of the related hydrido complex CpWH(CO)3 led to the related WIV trihydrido CpWH3(CO) via a coordinated dihygrogen complex. 40

complexes has also developed. The crystal structure of CpW( PR2) (CO) 2 reveals a planar phosphorus atom. 41 The reaction chemistry of the phosphavinylidene complex ( 7 ) has been described. The addition of species such as EtOH occurs across the P-C double

The chemistry of phosphorous ligands in cyclopentadienyl

n-Cyclopentadienyl, r-Arene, and Related Complexes 355

bond. 42 Finally the delightful pentaphosphacyclopentadienyl complex ( 8 ) may be isolated from the reaction of Cp2Cr2(C0)4 with Pq under thermal conditions.43

complex to Cp2Mo2(C0)6 to give (9). 45 In a related reaction the tied dimer (10) is generated from the hexacarbonyl parent complex by reaction with P2Meq.'l Unsaturated M-P bonds can also be used as ligands to generate complexes such as (11) .52

insertion of CH2 into the Cr-C1 bond of CpCr(N0)2C1.44 As with phosphorus, the chemistry of cyclopentadienyl complexes containing sulphur ligands is considerble. Simple reactions of CpCr(C0)2S(C0)2CrCp have been described46t47 as has the extension to the chemistry of the selenium analogue. 48 The triply-thiol-bridged dimer [CpMo(CO) (p2-SMe)3Mo(CO)Cpl+ has been made 49 and the reactions of [CpMo(p-S)]2S2CH2 with acetylenes and olef ins described. 50 Polyhydride polyalkylated cyclopentadienyl complexes have been investigated including [Cp*WH4 12. 53

The bridging PhPPPh unit has been introduced via a nickel

Reactions of nitrosyl Cp complexes include the Cu-catalysed

2.4 Manganese and Rhenium: The effect of introducing the powerfully electron-withdrawing CF3 group to the cyclopentadienyl ring in a series of complexes including (C5H4CF3)Mn(C0)3 and also Fe,Rh and Ir complexes has been examined.54 A reexamination of the reaction of CgHMeg with M I I ~ ( C O ) ~ ~ has shown that two products are generated . The expected CpMn(C0)3 ( 7 7 % ) and also (CgMe4H)Mn(C0)3 A large range of Mn, Fe, Ru, Rh and Ir complexes can be made using T ~ ~ [ C I ~ H ~ C H ~ C ~ H ~ ] as a source of the tied Cp rings.56

optically active with metal-centred chirality has been claimed for [CpRe(NO)(PPh3)]PFg. Reactions of this substrate with Lewis bases has also been described.57

A theoretical study of nucleophilic attack on the related complex [CpRe(NO) (CO) (PPh3) 1' led to the conclusion that primary attack occurs at the NO ligand followed by migration.58 A theoretical study of [Cp3Re306I2+ has led to the prediction of a triplet ground state.59 The study also examined the related [ (hmb) 3M3X6 I '+ (X=halogen) complexes of the early transition elements.

The first observable transition-metal based Lewis acid that is

Two reports involve the reactions of the cyclopentadienyl


Ph (9 )

co Fe(CO1,

(11)

co (1 3)

R u

+ I

(10)

(12 1

(1 4)

co'/ % /

/ co

(15) (16)

n-Cyclopentadienyl, n-Arene, and Related Complexes 357

rings in rhenium complexes. CpReH(SiPh3) (C0)261 initial deprotonation of the ring is followed by R or SiPhj migration to give the final products. The and &s/trans isomerisation of the Re111 complexes Cp*Re( CO) 2x2 has also been examined, 62

In both C P R ~ ( N O ) R ( P P ~ ~ ) ~ ~ and

The properties of high oxidation state rhenium complexes has received considerable attention. the presence of PPh3 to generate fur an^.^^ When treated with LiAlH4, Cp*ReOC12 is converted into Cp*ReH6 with a structure based on a pentagonal bi~yramid.~* Lastly, treatment of Cp*ReO(O2CCR2) with CO leads to (12) via elimination of C O Z . ~ ~

has been reported. In the case of CpRe(PMe3)3, photochemical displacement led to C-H activation of both alkenes and alkynes at low temperatures and cyclometallation products at higher temperatures.66 With Cp*Re(CO) (PMe3)N2, photochemical activation &a N2 loss led to activation of C-H bonds.67 Photolysis of CpRe(PPh3)2H2 led to loss of PPh3 and H/D exchange was observed.68

Cp*Re03 reacts with acetylenes in

Carbon-hydrogen bond activation by.a number of Re complexes

2.5 Iron,Ruthenium and Osmium: A new cyclopentadienyl ligand is generated together with an unsaturated phosphorous ligand when (C0)4Fe-P(CgMeg)C(SiMe3)2 is allowed to undergo intramolecular rearrangement to give (13). pentadiene undergoes a cyclisation when reacted with RuHCl(PPh3)3 to give the known CpRuCl (PPh3) 2. 70

extensively studied. When CpzFe(C0)~ is photolysed at low temperatures CO loss leads to CpFe(C0) ( q3-Cp) .71 Two isomers of this complex were identified. An examination of the photochemistry of Cp2Fe2(C0)4 has shown that Cp2Fe2(C0)3 is the intermediate in photochemical substitution of CO by MeCN.72

the cis isomer and measurement of the activation energy barrier to the isomerisation process. 73 The same Cp2Fe2 (CO) 3 has been proposed as an intermediate in the catalytic addition of halocarbons to alkenes. 74

The related bimetallic fulvalene complex (C~OH~)RUZ(CO)~ has been reported and its chemistry e~amined!~'~~ Bimetallic complexesbasedon 6,6-diphenylfulvene such as (14) have also been reported.77 Useful sources of the CpRu fragment such as

69 It has been shown that 1,4

The photochemistry of cyclopentadienyl iron complexes has been

A study of the Cp" analogue has led to the identification of


CpRuX( COD) (COD= cyclooctadiene) have been developed78 7 9 as have new sandwich complexes such as the Ru( IV) complex (15). An additional complex containing a weakly bound H2 complex has been made by protonating CpRuH(PPh3) (CNtBu) at OC.81

to deoligomerise silan has been demonstrated.82 The insertion of ethylene into the CpFe-SiMe3 bond has also been examined for implications for transition metal catalysed hydrosilation of a l k e n e ~ . ~ ~ Useful CpFe substrates such as [Cp*Fe(CO) (PMe3) (THF) ]PFG~* have also been described.

cyclisation v i a a simple Friedel-Crafts reaction giving (16) which is derived from the parent benzyl Other reactions reported for the CpFe fragment include the first report of an arsalkenyl complex (17)86 and migration of the phenyl group of the phosphoramide to the metal to generate (18) .87

The use of CpFe-containing complexes with polysilane ligands

Substituted Cp rings can be made to undergo intramolecular

2.6 Cobalt, Rhodium and Iridium: The pentaphenylcyclopentadienyl ligand has been the subject of three different reports, all based on complexes of the form (C5Ph5)M(C0)2 (M=Co or Rh) made for example by the reaction of Na(CgPh5) with [RhC12(C0)2] 2. both been examined. A comparison with the pentabenzylcyclopentadienyl complexes has also been made.

The reaction of LiCp* with Cox2 (X=halide) has been used to generate dimeric complexes of the form [Cp*CoXl2 in which strong antiferromagnetic interactions have been observed. The report also described the chemistry of the paramagnetic monomeric complexes

The structure88 and electro~hemistry~~ have

CP*COXL. 91 Lithium or potassium indenyl has been used to generate both

iridium complexesg2 form (r1~-indenyl)Rh(CNR)2.~~ Bimetallic complexes of Co,Rh and Ir have been made using thallium fulvanate T ~ ~ ( C I O H ~ ) . ~ ~ With the linked permethylcyclopentadienyl lithium reagent dirhodium complexes such as (19) can be made.95

migration of the metal gives [Cp’Ir(CH3) (P(CgHqF)3)2] +,96

Hydrogen migration to and from the Cp rings has been observed with the rhodium complex [CpRhH(CO) (PR3) The electrochemistry of protonation products of CpCo(PR3)2 complexes has been examinedg8 as has the structure and dynamics of

and isocyanide rhodium complexes of the

Dehydrogenation of cyclopentane leads to (20) and subsequent


/OSiMe3 Fe - - A s = C

‘R co’/

c o (17)

kh= Rh

(1 9)

(21 )

(1 8 )

j4 1 L / Ir\ L

+

Rh


(indenyl)Rh(C2H4)2.” Both q5 and q3 indenyl complexes of Ir have also been reported.100

has been used to compare the structure of the iridium complex with the rhodium analogue.’” The barrier to rotation of the fulvene ligand in [ (CsH4CH2)Rh(COD) 1’ has been examined.lo2 In the case of [Cp*Rh(C0)2]2 both the radical anion and dianion were identified in the reduction chemistry.lo4 A study of the radical anion of [CpCo(CO)l2 has led to the postulate that the extra electron is primarily in an antibonding 0rbita1.l’~ Cp*Ir(C0)2 has been used as a basic metal-containing complex in metal-metal bond forming reactions.lo6 The synthesis and esr spectra of [Cp’CoLJTCNE (L=CO, PR3 or pyridine) complexes have been examined. lo3

A low temperature neutron diffraction study of Cp*IrH2(SiMe3)2

The bisethylene complex CpCo(C2H4)2 reacts with PhMgBr in the presence of TMEDA (tetramethylethylenediamine) to generate the novel adduct(21) . Io7 In a different report, the same substrate has been reacted with acetylenes to generate q6-arene complexes and other acetylene condensat ion products. lo* Photolysis of CpfCo(C2H4)2 in the presence of AsqSq generates a number of products such as (22),lo9

The use of cyclopentadienyl rhodium and iridium complexes for C-H bond activation remains a fertile area of study. Reports include the isomerisation of hydroalkylrhodium complexes formed by oxidative addition of alkane C-H bonds to Cp*Rh centres and C-C bond activation by isomerisation of alkylhydridorhodium complexes. A deuterium isotope study of the arene/aryl equi 1 i br ium for Cp*RhH ( CgHqMe ) PMe3 showed that the inter conver s ion was a lower energy process than dissociation of the arene.’” Inversion at the chiral Co centre of (23) has also been investigated.’l2 Vinyl hydride complexes have been isolated when the bisethylene complex CpIr (C2H4) 2 is phot01ysed.l~~

addition of CH2C12 to a nonporphyrin cobalt(1) species has been observed for Cp*Co(CO) z1I4. Rh116 bisethylene complexes CpM(C2H4)2 of Cp“ are reacted with tBuC=P, diphosphacyclobutadiene ligands are generated(24).

In a related photochemical reaction the first oxidative

When either the Coil5 or

n-Cyclopentadienyl, n-Arene, and Related Complexes 36 1

2.7 Nickel, Palladium and Platinum: Flexibility of cyclopentdienyl coordination has dominated the reports of this group of metals. Nickelocene is a useful source of the CpNi moiety and the PH3 ligand is generated in the reaction of Cp2Ni with PH4I to give CpNiI(PH3) ring from (CpPdPEt3)z using Me3SiC1 gives halobridged complexes such as (25) amongst other products.’l8 Two reports involve q5 to ,I’ transformations. product containing the ql-Cp ring CpPd(CgHqN2Ph) (PEt3)2 may be isolated as well as products in which the Cp ring is completely cleaved from the 1neta1.l~~ Related ,I’ and ql-Cp platinum phosphine complexes have also been made. 1 2 0

Cleavage of a bridged cyclopentadienyl

When CpPd(NPhNCgH4) is treated with PEt3 a

2.8 Lanthanides and Actinides: The ytterbium monocyclopentadienyl dialkyl complex Cp*YbCl( t B ~ ) 2 can be made by treating YbC13 with NaCp* and LitBu.121 The lutetium complex can be formed analagously The structure of the 7-coordinate complex (26) has been determined in which pentagonal bipyramidal geometry about the U is found.122

3 Biscyclopentadienyl Complexes

3.1 Titanium, Zirconium and Hafnium: A route to mixed ring complexes of Ti has been reported using the initial disproportionation of Cp2TiC12 with Tic14 to give CpTiC13 followed by reaction with a substituted sodium cyclopentadienyl to give CpCp’TiC12.123

cyclopentadienyl rings can be made utilising C5HMeqSiMe2CgHMeq and the related CgHMeqSiMe2 (CH2) 2Si ( M ~ ~ C S H M ~ ~ ) ? ~ ~ tBu substituted complexes can be generated by methylating dimethylfulvalene with MeLi followed by reaction with the appropriate metal halide. 125

Reductions using sodium amalgam involving the coupling of the cyclopentadienyl rings of Cp2MC12 complexes have been reported for Ti126 and Zr.127 Oxidation of the titanium complex with molecular oxygen gives the 0x0-bridged dimer (27). In contrast to the Cp-coupling reactions, reduction with magnesium in the presence of PMe3 led to C-H activation to generate (28)

clusterification reactions involving loss of the cyclopentadienyl ring.

Complexes of a range of metals including Ti and Zr with tied

There are now a considerable number of reports of

Those include the reduction of Cp2TiC12 with Li3N to give


E t 3P-Pd- Pd -P E t, \ /

CI

(25)

Ti Ti

( 2 7 )

(29 )

MeCN, I H N C M e -NCMe

MeCN/ "I ~r I Br

(26)

+

(28)

CP

CO-CO

/ \ CP CP

(30)

n-Cyclopentadienyl. n-Arene, and Related Complexes 363

products including Cp8TigN, characterised by mass spectra.12’ Hydrolysis of Cp2Ti(CO)2, or reaction with H2S gives CpgTigOg or ~ p g ~ i g ~ g respectively . ’30 While [Cp3Ti3(OMe)3(p2-OMe)3(p3-O) 1’ is the reported product of the reaction of [Cp2Ti(H20),]+ with MeOH.131

orbital calculations have been carried out on Cp2TiX2 (X=Br,I)132 and mass spectral fragmentation studies have been reported f o r the titanocenophane dihalides Me2Si(CgH4)2TiX2 (X=Cl,Br, I) .133 Electrogeneration of the paramagnetic anion [Cp2MC12]- (M=Zr or Hf) has been re~0rted.l~~ Substitution reactions of CO for Cp2M(CO)2 (M=Ti,Zr or Hf) have been studied and found to be dissociative for Ti and associative for Zr and Hf. The difference in mechanism is ascribed to the size difference of the metals. 135

example, the bimetallic activation of C02 ( 2 9 1 ~ ~ ~ and the reaction of CpzTi(C0)~ with CpCo(C2H4)2 to give (30).137 The ligating properties of the other chalcogens have also been exploited. Dichalcogen chelates such as the first ditellurium ligand (31)138 and a range of analagous selenium complexes on Ti,Zr Hf, Mo and WI3’ have been reported. different selenium complex CpzTiSeg has been made in an electrochemical synthesis and shown to provide a soluble source of selenium.140

Photoelectron spectroscopic studies together with molecular

The oxophilicity of the Cp2M fragment is demonstrated in, for

An entirely

The lability of both CO and PR3 ligands when coordinated to the Cp2Ti unit has been exploited to generate compounds containing nitrogen-based ligands. When Cp2Ti(C0)2 is treated with N4S4 a range of products may be isolated including the structurally characterised TiN4S3 and TiN2S3 rings.141 The reaction of CpzTi(PMe3)~ with diphenyldiazomethane leads to substitution of one phosphine and simple adduction of the dia~omethane.’~~ Other labile ligands have also been examined in this system for example Cp2Ti(CF3S03)2. The substitution of the trifluororsulphonate ligands is facile143 and the related zirconium system has also been examined. 144

hydrogenolysis of Cp2ZrX(CH2CMe3) complexes to generate C p ~ 2 r H X . l ~ ~ Applications to organic synthesis have also appeared including the use of Cp~Zr”Bu2 as a source of Cp2Zr

Ring-mediated H transfer reactions have been proposed in the


for cyclisation rea~ti0ns.l~~ The related cation [Cp2Zr(Me)(THF)]BFq has been used for ethylene polymeri~ationl~~ and the peroxyhafnium complex Cp2*HfR(OOtBu) used to demonstrate intermediates in the epoxidation of allylic alcohols.148

3.2 Vanadium, Niobium and Tantalum: An entry into Cp*2Ta chemistry has been developed with the reaction of Cp"TaCljPMe3 with LiCp*.14' The complex Cp*2Nb(BH4) provides an appropriate entry into Cp*2NbH3 chemistry.150 A study of the electrochemistry of Cp2NbC12 has led to the identification of the one-electron reduction product [Cp2NbC13NbCp2]- and [Cp~NbC1]2 on the way to n i ~ b o c e n e . ~ ~ ~ Reactions of mono and dihydr ides of CpzTaH( CO) have also been in~estigated.'~~ The exceptional stability of Cp" complexes is elegantly demonstrated in the indentification of a series of Cp*2TaHX (X=CH2,O,CCH2 and CH20) ~omp1exes.l~~ When Cp2*VX2 is reacted with NO, two oxidative ring cleavage products may be identified Cp*VC120 and [Cp*VI212(1~-0)

associative CO exchange, CpV( q5-pentadienyl) (CO) shows dissociative exchange.155 The related indenyl complexes (indenyl) 2V react with CO to give products such as q3, q5 (ind)2V(C0)2 the first example of ring slippage in a metal radical species.156 Biological applications include an investigation of the interactions of Cp2VCl2 with DNA constitutents which are very different from the interactionswith the better known antitumour agent cis-platin.157

In contrast to the 17-electron Cp'2V(CO) complexes which show

3 . 3 Chromium, Molybdenum and Tungsten: The structure of the dinuclear molybdenum complex (32) has been described158 as has the formation of cyclopentadienyl-bridged heterobimetallic complexes such as

presented f o r agostic interactions in tungstenocene dialkyl cations.16' The reduction of CpzMoC12 with Na/Hg in MeCN has generated the first q2-bound nitrile complex Cp2Mo( q2-NCMe) that has been structurally characterised.161 Doubt has been cast on the isolation of the MO and W oxychloride complexes such as Cp**M00C12,~~~ An infra red and Raman study has been carried out on solution and matrix isolated metallocene hydrides such as

Cp2MH2 (M=Mo or W) and [ C p ~ R e H 2 1 + . ~ ~ ~

( 33) .I5' Electrochemical evidence has been


3.4 Manganese and Rhenium: An examination of the high/low spin equilibria of alkyl-substituted manganocenes has been made using ’H and 13C nmr and interpreted in terms of slow exchange at low temperatures changing to rapid exchange as the temperature is raised.164 A doubly charged ion mass spectral study of metallocenes of Mn, Fe, Cp and Ni has revealed the only metal-containing ion to be Cp2M2+.165

3.5 Iron,Ruthenium and Osmium: New high-yield syntheses of ruthenocene and osmacene and substituted derivatives have been described.166 Syntheses of new ferrocenes include the spiral complex (34)167 for which the cobaltacenium complex has also been described. The synthesis and structure of the substituted ferrocene containing a norbornane substituent has been examined .168

The per-br idged f er rocenophane has also been reported. 16’ Both the synthesis and structure of (CgHPh4)zFe and an electrochemical study of the complex has been described.17’ One of the Cp rings in ferrocene can be displaced with AlCl3 in the presence of phosphabenzenes to generate cationic mixed sandwich complexes.171 The application of physical methods to the study of ferrocenes include a Mossbauer study of triarylstannylferrocenes, 172 a photoelectron study of 1,l’-disubstuituted f e r r ~ c e n e s l ~ ~ and Mossbauer and nmr spectroscopic studies of monophosphaferrocenes

study of the magnetic properties of [Cp*zFeI [TCNE] preparation and structure of the related [Cp*pFe] [C(CN)31 complex has also been described.176 The use of the ferrocenium cation as a one electron oxidising agent177 includes the synthesis of a large range of [ (indenyl)Fe(CO)2L]+ c0mp1exes.l~~ Studies of mixed-valence biferrocenium cations have been ~ep0rted.l~’ The structure of the mixed-valence complexes has been examined with the FeBrq- anion showing room temperature localisation of the Fe(1I) and Fe(II1) sites.’*’ A study of how the counter anion effects intramolecular electron transfer has also been carried out.

Dominant ferromagnetic interactions have been observed in a The

An important part of metallocene chemistry remains the use of the metallocene group as a ligand. and f e r r ~ c e n e l ~ ~ cyclophosphazene complexes have been reported. Direct tungsten-carbon bonds can also be generated to give

Thus both ruthenocene182


PR3 \

( 3 3 )

(3 7)

( 3 5 )

\

T@ C r

co ’ co I ‘co (45 1

( 3 4 )

( 3 6 )

C r

C r

( 4 6 )


molecules such as (35).184 The oxidation of such a complex CpW(N0)2(CgHq)FeCp to give the dioxo complex with displacement of both nitrosyl groups has been re~0rted.l~~ The phosphido complexes RP=M(CO)s insert into a C-H bond of ferrocene to give substituted ferrocenes .186

The formation of stacked bimetallic complexes has been discussed in a report of the reaction of ferrocenium with nickelocenium cations187 and the reaction of [CpFe(CqHqBPh)]- with Cr(NH3)3(C0)3 to attach the chromium to the boron-containing ring.188 Linking the rings of ferrocenes also remains a synthetic goal. The reaction of dilithioruthenocene with selenium gives (36).18’ The structure of the linked ferrocene (37) has also been reported.”’ The synthesis and fluxional properties of ruthenocene biscrown ethers has also been examined.lgl The protonation of bridged ferrocenes using strong acids has been investigated using nmr spectroscopy.192 Triflic acid has been used as a catalyst for Friedel-Crafts substitution of phosphaf er rocenes.

Other reports include the kinetic resolution of racemic allylic acetates in an asymmetric alkylation reaction catalysed by chiral ferrocenylphosphine palladium complexes and the use of the ferrocenyl group in peptide chemistry.lg5

3.6 Cobalt and Nickel: The formation of Cp2Co in the flash vacuum pyrolysis of CpCo(CO)2 has been reported lg6 and (CgHqPPh2)2Co has been investigated as a ligand.lg7 The synthesis of the first CgPhg nickel complex (CgPhg)NiCp has been achieved by the oxidative addition of CgHgBr to cyclopentadienylnickelcarbonyl .Ig8 The substitution of a Cp group in nickelocene has been exploited to generate CpNiMe(o1efin) complexes. 199

3 . 7 Scandium, Lutetium, Lanthanides and Actinides: An extensive series of permethylcyclopentadienyl complexes has been made by reacting sodium or potassium pentamethylcyclopentadienyl with the metal trihalides. 2oo. Products include adducts with the alkali metals. can be generated using the same reagents.201 The metal amide complexes M(NEt2)4 (M=Th, U) react with cyclopentadiene to generate a range of complexes CpnM(NEt2)d-n - ( n = l to 4).202 Using the tied ring (CgHq)SiMe2(CgHq) the ytterbium complex is a bridged

Tetrahydrofuran complexes such as Cp*zVCl (THF)


dimer in contrast to the other lanthanides in which the tied rings act as chelating ligands.203 Ring cleavage occurs when Cp2YCl(THF) is treated with KOMe to give CpgYg(OMe)4( v3-OMe)4( ~'-0) containing a 5-coordinate oxygen. 204 The synthesis and structure of the amido complex Cp*2YN( SiMe3) 2 generated from Cp*2YC1( THF) has been reported. 205 The desolvation of Cp*2M(THF)2 (M=Sm and Eu) has been used to generate the Cp*2M complexes both of which contain nonplanar cyclopentadienyl rings. 206 Photoelectron spectra and calculations for these complexes have been carried out showing the compounds to be highly ionic but giving no explanation for why the rings are nonplanar . 207 Other theoretical studies include an analysis of the CO insertion reaction into Cp*2MR2 complexes to generate (38) 208 and calculations on CpzTh( PH2) 2Ni (CO) 4 to probe the weak donor/acceptor relationship between Ni and Th. 209 Bond disruption enthalpies for Th or U-R bonds in Cp*2M complexes have been measured. 210

Reduction of (C5H3SiMe3)2UX2 has been carried out using Na/Hg to give the first U(I1I) halide bridged dimer.211 The first organoactinide polysulphide complex Cp*2ThSg has also been reported. 212 When Cp*2Sm( THF)2 is reacted with PhN=NPh, dimeric complexes may be isolated with agostic ortho-phenyl protons. 213

A series of phosphido complexes has been examined. The structure of Cp*2Th(PPh2)2 shows no evidence for significant Th-P multiple bonding.214 When the lutetium complexes (39) was structurally characterised it was shown to contain a puckered 4-membered ring. 215 The complex (40) has been proposed to contain a platinum-thorium bond. 216 Carbon-hydrogen bond activation including cyclometallation reactions have been reported for Cp*2ThR2 complexes. 217 The first enolate complexes of the type [Cp' 2Y (p-OCH=CH2) ] 2 have been described. 218

4 Tricyclopentadienyl Complexes: The structures of Cp3M (M= Er,Tm) complexes have been described, revealing three q5-Cp ligands per In contrast the structure of Cp3Lu contains infinite chains with two n5-Cp ligands and the metals bridged by ql-Cp ligands.220 The structure of Cp3La221 and the first Th(II1) structure has also been reported.222 An electrochemical study of Cp3M (M=Sm, Yb, Eu) complexes has revealed reversible reductive processes. 223 A theoretical and photoelectron spectroscopic study of Cp3UX complexes using

n-Cyclopentadienyl, z-Arene, and Related Complexes 369

nonrelativistic calculations has allowed an assignment of the spectra.224 Optical spectra of these complexes have also been described. 225

reported, resulting in CO bond activation. 226 The preparation of Cp3USnPh3 has allowed the characterisation of the 1st U-Sn bond227 while the reaction of Cp3UC1 with the polyhydride [ReH6(PPh3)2]- gives Cp3UH6Re(PPh3)2.228 The Structure Of Cp3UAlH4 has been shown to be a polymeric structure containing bridging [AlHqI- groups.229

The reaction of Cp3UCR2 complexes with W(CO)6 has been

5 Arene Complexes

5.1 Vanadium, Niobium, Tantalum and Zirconium: Mixed sandwich complexes of vanadium containing arene rings have been described in two reports. The bisindenylbisvanadium complex (41) has been structurally characterised and contains a metal-metal bond length of 2.35A. The complex is formed in the reductive dimerisation of bisindenyl vanadium by potassium. 230 The other report concerns the cleavage of the triple-decker sandwich complex CpV(Bz)VCp by LiCp followed by treatment with alcohol to give CpV(Bz) .231

An investigation of the electrochemistry of the cluster [ (hmb) 3NbjClg]+ has revealed three quasi-reversible oxidation processes. It is proposed that all the compounds generated retain the trimeric unit.232 The reduction of Cp2ZrC12 with Mg(anthracene) has been reported to give a zirconium anthracene complex. 233

5.2 Chromium, Molybdenum and Tungsten:Considerable attention has been directed at the process of arene exchange in arene chromium tricarbonyl complexes . labelled arene complexes it has been found that CO exchange accompanies arene exchange but free CO is not incorporated. 234 The use of styrene complexes demonstrated participation by the olefin both internally and externally in the exchange process. 235 A study of the thermochemistry of arene exchange has allowed an extensive tabulation of the metal-arene bond strengths. 236 Finally a kinetic study of arene displacement in (arene)Cr(CO)2(CX) (X= S or Se) has demonstrated that the rate of arene exchange is faster for both CS and CSe than for CO and it was proposed to occur by ring slippage.237

In one study of I3CO


The nucleophilicity of the sulphur in (toluene)Cr(C0)2(CS) has allowed adduction by Cr (CO) 5. 238 The oxidation of (hmb)M( CO) 3 (M= Mo or W) by I2 has allowed the isolation of the complex [ (hmb)M(CO) 31 1' and a series of polyhalometallate anions.239 The interaction of (arene)Cr(C0)3 with solvents has been examined using nmr spectroscopy. Particularly large upfield shifts are found for the aromatic hydrogens in aromatic solvents. 240 Other nmr spectroscopic studies include the investigation of relaxation times for 95M0, I3C and l 7 O in (arene)Mo(C0)3 complexes241 and a 13C nmr study of cyclophaneMo( CO) 3 complexes. 242 Intramolecular rotational processes have been examined by nmr in the (C6Et6)M(C0)2L (L= CS or PR3) complexes. 242

demonstrated that the process becomes reversible as the temperature is lowered. 243 Haptotropic shifts in polycyclic complexes is also an active area of research. The energy barrier of the ring-to-ring slip of the Cr(C0)3 moiety in (naphthalene)Cr(CO)j has been estimated at 140 kJmol-1. 244 When the thermal rearrangement of the chromium from the B-membered ring to the 6-membered ring was examined in ( 4 2 ) it was found that decomplexation of the ring is a competing reaction and the relative ra-tes are solvent dependant. 245 When Cr (NCMe) 3 (CO) 3 is reacted with benzofulvenes both n5 and q6 complexes result. 246 Reduction of (naphthalene)Cr(C0)3 followed by protonation leads to the n5 ~omplex(43).~~~ In the case of (n6-fluorene)Cr(C0)3, treatment with base followed by alkylation gives exo-addition at low temperatures. 248

applications to synthetic organic chemistry. A study of nucleophilic and electrophilic substitution reactions of conformationally restricted (arene)Cr(C0)3 complexes has shown that nucleophiles react at carbons eclipsed by Cr-CO bonds and electrophiles at staggered postions. 249 Both the stabilisation of a-carbocations 250 and reactivity of a-hydrogens towards base251 has been investigated. alkyllithium reagents has been studied252 and measurements of acidities carrried out. 253

stereochemical control of substitution processes254 and three

An electrochemical study of the oxidation of BzCr(C0)3

The major area of (arene)Cr(C0)3 chemistry however remains

The substitution of arenes with

The use of bulky SiMe3 groups has been used to direct

rr-Cyclopenladienyl, n-Arene, and Related Complexes 37 1

reports255' 2 5 6 r 2 5 7 discuss the use of halogen-substitiuted arenes in substitution chemistry. A spectroscopic investigation of ( 4 4 ) has presented little evidence for electron delocalisation between the rings.258 The structures of the silicon substituted complexes ( 4 5 ) have been investigated.259 Other studies of substitution substitution reactions on (arene)Cr (CO) 3 c o m p l e ~ e s ~ 6 ~ * ~ ~ ~ have concentrated on regiodirection260 and tele-substitution. 261

Bisarene Comp1exes:The new triple-decker-sandwich complex ( 4 6 )

has been proposed as a product of a metal vapour synthesis of chromium with mesitylene. 264 The metal vapour technique has also led to the isolation of (CtjH~As)2Cr.~~~

and the second one-electron removal demonstrated to be quasi-reversible. 266 Radical cations of both ( 4 7 ) and ( 4 8 ) have been r e p ~ r t e d . ~ ~ ~ , ~ ~ ~ Ligand reactions on (arene)ZCr complexes include nucleophilic substitution, 269 decarboxylation 270 and substitution reactions of oxidised species. 271 Bisbenzene chromium has been attached to cycloph~sphazenes~~~ and chromium and molybdenum incorporated into polysilanes containing phenyl groups. 273

The oxidative electrochemistry of (hmb)2Cr has been examined

5.3 Manganese and Rhenium: When manganese or rhenium is co-condensed with arenes and PMe3, dimeric complexes such as [(arene)Re(PMe3)2]2 may be isolated. Hydrogenation leads to cleavage and the formation of mononuclear complexes such as (arene)MnH( PMe3) 2. 2 7 4 Similar complexes can also be made from ReH7(PPh3)2 when treated with an appropriate hydrogen acceptor in the presence of an arene?75'276 The complex (Bz)ReH(PPh3)2 photodissociates PPh3 giving intermediates that will activate C-H bonds. 277

C-H bond activation also occurs when rhenium is co-condensed with alkyl substituted aromatics such as toluene (50) .278 When rhenium is co-condensed with benzene and cyclooctadiene the mixed sandwich complexes (51) may be isolated279 and with indene the n 6 indeneq6- indenyl rheniurn complex results. 280

Reports of the chemistry of (arene)Mn(C0)3 chemistry include a full report of the synthesis of the derivatives (arene)MnX(C0)2 (X= halogen).281 In the case of (hmb)MnH(C0)2, reaction with CO has been reported to yield H-migration to the hmb ligand. while with BzMnR(C0)2, treatment with PR3 is reported to give

282


F\ / N =

/p\ F N-

(49)

( 5 0 )

4+

(52) (51)

n- Cyclopentadienyl, n-Arene, and Related Complexes 373

migration to the arene ligand when R=alkyl but not hydrogen.283 Other reports concentrate on nucleophilic addition to arenes in [ (arene)Mn(C0)3]+ complexes284 and forcasts of the activation of arenes via CO stretching force constants. 285

5.4 Iron, Ruthenium and Osmium: Co-condensation of arenes and osmium has allowed the characterisation of bisbenzeneosmium and analysis of intramolecular ring exchange processes. 286 In the case of the condensation of iron with toluene, the bistoluene iron complex may be reacted with ethylene at low temperatures to give (toiuene)Fe(C~Hq) 2 which decomposes at -2O.c. 287 Mixed ring arene/carborane iron complexes can be made using a similar approach.288 The codeposition of iron and benzene in an argon matrix has led to a report of BzFe, BzFe2 as well as Bz~F~.~*' When the metal vapour method is applied to ruthenium, complexes such as [BzRu(CO) ( v3-C6Hg) ]BFq may be chara~terised.~~' A new ruthenium benzene cluster ( v6-CgH6)Ru3 (CO) 7 (NPh) has been isolated by heating Ru3(C0)12 with nitrobenzene in benzene.291 The use of [RU(H20)6l2+ as a source of the metal for sandwich complexes has allowed the synthesis of (arene)Ru( v5-C8Hll) .292 Reaction of RuH2(PPh3)4 with H ~ C ( S O Z C F ~ ) ~ in the presence of arenes generates [ (arene)RuH(PPh3)21t complexes.293

The photolysis of Os(CO)5 in benzene has led to (n2-C6H6)0s(CO)4 which is said to be similar to, but more reactive than, the iron analogue 294 The dimeric halide complexes [(arene)MX2]2 (M= Ru, 0 s ) remain a useful entry into arene complex chemistry. The development of the ligand chemistry of these complexes continues. 295-300 These substrates have also been used to make metalloborane complexes,301 used as catalysts for the coupling of furans and thiophenes302 and simple derivatives such as [ (p-~ymene)20~2(OH)3]+ used for the catalytic oxidation of aldehydes to carboxylic acids. 303

Simple derivatives such as (p-cymene)OsC12(DMSO) have been reported304 and the substitution chemistry of [ (arene)RuL3]2+ complexes explored. 305, 306 The synthesis of cyclophane ruthenium sandwich complexes has been achieved to give m o n o n ~ c l e a r ~ ~ ~ and triple-decker-sandwich complexes ( 52) . Reduction of (52) has been reported to give the Class I1 mixed-valence dication containing Ru(0) and Ru( 11) .308

used to difunctionalise hmb309 and other arenes310 Double nucleophilic addition to [Bz~Fe12f complexes has been


Q F t

( 5 3 1

Ru

. . c o


generating cyclohexadienes. With the neutral BzzFe, arene displacement can be utilised to generate complexes such as (53) .311 The related ruthenium complex (54) has also been reported. 312

r e p ~ r t e d ~ ’ ~ , ~ ~ ~ and the reaction with superoxide to give dienone complexes discussed. Most attention to this class of complex has focussed on nucleophilic addition to the arene ligand. 315 316 In the case of chlorobenzene complexes , substitution reactions3’’ 1 318, 319 with nucleophilies such as LiSnPh3320 have been studied. Arene displacement reactions have also been examined for the neutral 17-electron complex CpFeBz. 321 The quantum yield for photochemical arene release decreases with the level of methylation of the Cp ring.322 and a range of different arenes such as naphthalene and anthracene have been investigated. 323 A study of substituted areneFeCp radical complexes and dimerisation products has been made. 324 The oxidation of dimeric complexes such as (55) has also been investigated .

Two preparations of [ CpRu(arene) 1’ complexes have been

5. S Other Arene Complexes: The reaction of [Cp*CoC12]2 with PhLi gives a trimetallic biphenyl complex (55) 326. The structure of the trimer [ B z ~ C O ~ ( C O ) ~ I B P ~ ~ has also been reported.327 The use of (arene)NiR2 complexes for isomerising l-butene has been examined. 328 The migration of the metal between the rings of (56) has been watched and an estimate of 88

kJmol-l placed on the barrier to the migration process.329 Both dimetallic and trimetallic chloro-bridged uranium

hexamethylbenzene complexes have been reported330 331 and the structure of the first lanthanide arene complex (hrnb)Sm(AlC13)3 descr ibed ,


1. 2.

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32.

33.

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35. 36.

37.

38. 39. 40.

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x-Cyclopentadienyl, x-Arene, and Related Complexes 38 1

1 9 3 . 1 9 4 .

1 9 5 . 1 9 6 .

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2 0 0 .

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2 4 2 .

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247. 248 .

249 . 250.

2 5 1 .

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J.R. Gilday, D.A. Widdowson, J- Chem. SOC., Chem. Commun., 1 9 8 6 , 1 2 3 5 . F. Rose-Munch, E.Rose, and A. Semra, J- Chem. Soc., Chem. Commun., 1 9 8 6 , 1551. J.P. Gilday and D.A. Widdowson, Tet. Lett., 1 9 8 6 , 21, 5525 . N.J. Gogan, I.S. Jayasinghe and P.K. Sayal, J- Organomet. Chem.,

N.I. Kirillova, A.I. Gusev, V.A. Sharapov, O.B. Afanasova, Y.E. Zubova, N.V. Alekseev, E.A. Chernyshev and Y.T. Struchkov, J- Organomet. Chem. 1 9 8 6 , 306, 5 5 . M. Stobbe, 0. Reiser, T. Thiemann, R.G. Daniels and A. de Meijere, Tet. Lett., 1986 , 21, 2353 . F.Rose-Munch, E. Rose and A. Semura, J- Chem. SOC. , Chem. Commun., 1 9 8 6 , 1108. M. Uemura, T. Kobayashi, K. Isobe, T. Minami and Y. Hayashi, J- grg. Chem., 1 9 8 6 , 51, 2859 . J. Brocard and J. Lebibi, J- Organomet. Chem., 1 9 8 6 , 310, C63.

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-___

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15 Homogeneous Catalysis by Transition-metal Corn pl exes

BY M. BOCHMANN

1 General

Several books have appeared on the subject of homogeneous cata lys is ,

deal ing with "Metal Clusters i n Catalysis"1, "Palladium Reagents i n Organic Synthesis" ( inc lud ing c a t a l y t i c pal 1 adium reactions 12, and "Hydrogenation

Methods", which contains some references to homogeneously catalysed hydrogenations.3 Volume 3 of "Mechanisms of Inorganic and Organometall i c

Reactions"4 includes a chapter on homogeneous ca ta lys is by metal ions and covers the l i t e r a t u r e from J u l y 1982 t o December 1983. Two monographs deal

w i t h supported organometall i c cata lysts : Y. Iwasawafj, and "Supported Metal Complexes:

by F.R. Hartley6, which covers hydrogenations, CO reactions, C-C bond

formations, hydros i l y la t ion , ox idat ion and hydrolysis. Coordination Cata lys is i n Organic Chemistry" gives a mu1 ti tucle of examples of

se lec t i ve reactions and t h e i r appl icat ions to organic ~ y n t h e s i s . ~

number of i n t e r e s t i n g accounts on homogeneous and phase-transfer ca ta lys is

covering carbonylat ions (H. Alper), enant ioselect ive ca ta lys is (H. Rrunner), C-C bond formations (G.P. Chiusol i ) , S i - H and C-H ac t i va t ion (W.A.G. Graham), metathesis (R.R. Schrock) and 25 years i n the organic chemistry of palladium (J. Tsuj i) .8

A review gives an overview over the cont r ibu t ion of organometallic ca ta lys is t o industryg, another i n the ser ies on t r a n s i t i o n metals i n organic synthesis covers CO reactions, hydrogenations and oxidations.1° The r o l e of zirconium ca ta lys ts i n hydro- and carboalumination of alkenes and alkynes, cyclopropanations and diene ol igomerisations has been discussedll , and an account deals w i th the r o l e of e l e c t r o p h i l i c metal carbenes i n cyclopropanations and other synthet ic appl ications.12

"Tai lored Metal Catalysts" by a New Generation of Catalysts"

The "Handbook of

Volume 300 o f J.Organomet.Chem. i s another ' 'special issue" and contains a


385


C6D5

+ CH3D + CHZD, + CHD, (Eq. 1 ) (30'/.) (lo'/.) (traces)

(1 1 E = S , S e ; R = Me, Et, Pr', Ph, etc.

R h C 1 L, ( P h, P-0, CCH= CMe 2 1 + R 2 C=CH C02 H

Ar

L

L = PPh3

/c+ Cp2Zr--PPh2 +

Ph d o f H2

H, "Cp2ZrmH" + PPh,Me (Eq. 3 1

OH

4 91'/0 (Eq.4) Ph \ [ I r H2L4 1'

L = P h 2 P - p * I 7.4OI0 e.e.

Homogeneous Catalysis by Transition-metal Complexes 387

2 Hydrogenations and Reductions

I r o n atoms i n a C2D, matr ix catalyse HID exchange w i th co-condensed 01efins.~3 The H/D exchange between C6D6 and H2 i s catalysed by (C6H6)ReH(PPh3) under photo ly t i c condit ions. Only aromatic D i s H/D

exchanged.14 I rH5(PPr i 3)

CH, and C6D6 (eq.11.15 S imi la r ly , H/D exchange w i th C ~ D ~ and saturated

hydrocarbons occurs i n the presence of CpReH2(PPh3),; (895) f o r a-H of THF.16

presented, f o r example during the react ion of dienes w i th CpFe(C0) ,H.17 The rad ica ls Co(C0); and Mri(C0); may be present i n hydrogenations and hy d r o f o rmy 1 a t i on s .I8

A 1:l mixture of Cp2Ni and LiAlH, i n M F acts as "homogeneous Raney n i c k e l " and reduces o le f ins, dienes and alkynes to saturated hydrocarbons.19

The se lect ive hydrogenation of non-conjugated dienes t o monoolef i n s i s

catalysed by Ru2(cod) ,(02CCF3),( p--02CCF,),( p-OH). reduced to cyclooctene; reduct ion only occurs once a l l the diene has been consumed.20 By contrast,

pal ladium complexes i n the presence of the fer rocenyl l igands (1) reduces conjugated dienes to monoolef ins, 2. 1,3-cod to cyclooctene.21

HN(CH2CH2PPh2),RhC1 has been studied; the coord inat ion of the o l e f i n i s the

rate-determining step.?? S imi la r invest igat ions of the reduction of cyclohexane have establ ished a dihydride complex as react ive intermediate.23

The r a t e of l-hexene hydrogenation catalysed by RuCl 2(Ph2P(CH 2)n_-PPh2)2 increases i n the order 1 = 1 > 2 > 3 and proceeds only i n po lar solvents.24

The k i n e t i c s of o l e f i n hydrogenation by a series of cat ion ic Rh complexes w i t h c h i r a l and non-chiral chel a t i n g l igands have been measured.25 Not only phosphine l igands give c a t a l y t i c a l l y ac t i ve complexes: complexes, too, are excel lent ca ta lys ts whose a c t i v i t y i s inf luenced by the amine substituents.26

the reduction of h igh ly subs t i tu ted alkenoic acids by ca t ion ic Rh complexes i n the presence of base (eq.21.27 The se lec t ive reduction of C=C bonds i n a,$- unsaturated carbonyl compounds i s achieved using a RhCl 3 /A l iqua t R-336 two-phase system. Solvated ion pa i rs [(C,H,,) 3NMe]+RhC1 ,+- are formed.28 This system a lso catalyses the reduction of naphthalene t o tetrahydro-naphthalene.29 I o n i c b i p y r i d y l and phenanthroline complexes of Rh, Ir and Fe may act both as hydrogenation and phase-transfer b i func t iona l catalysts.30

i s a slow c a t a l y s t f o r the H/D exchange between

turnover i s highest

Evidence f o r the involvement of rad ica ls i n o l e f i n hydrogenation has been

1,5-cyclooctadiene i s isomer icat ion does not take place, and f u r t h e r

The mechanism and thermodynamics of the hydrogenation of l-heptene by

Rh aminopyridine

Intermediate chelate formation <a t rans-es ter i f i ca t ion i s responsible f o r


C I O C O C H 3 4 0 COCH3 ( 90 '10 1

Scheme 1

0 0 I I I I

/ \ R ' - C - C - C - O w /

R R

(5) . n = 1,2

Pd Ln BugSnH

0 0 I I I I / \

R'- C-C-C-OSnBug

R R

(6 ) * R m e n t h y l , X = 0, N P h

Pd /PBu3

HCOOH/Et3N IOOO/. conversion (Eq. 6) 10Oo/. selectivity


Olef ins are r a p i d l y hydrogenated by anion-promoted Rug c lus te rs such as

[Ru,(CO) l,(NCO) I-; the react ion i s suppressed by C0.31 The mechanism has been e luc idated using Os3 model compounds which are only poor catalysts.32 Other 0s c lusters , 3. CpNiOs3(pH) ,(CO) 9, are more su i tab le f o r isomerisations than f o r o le f i n h y d r ~ g e n a t i o n . ~ ~

o f 1,3- and 1,Scod t o cyclooctene i s achieved w i th a Z r ( I I 1 ) c a t a l y s t (eq.3) which i s more ac t ive than Zr(1V) hydrides.

lS2,3,4-tetraphenylbutane exclusively.34

OsCl (OAc)(CO)(PPh3) 2, are h igh ly ac t i ve ca ta lys ts fo r the hydrogenation o f aldehydes and ketones. The a c t i v i t y i s in f luenced by the anionic ligands.35 A dimeric Ru hydride (2) has been s t r u c t u r a l l y characterised which hydrogenates cyclohexanone a f t e r d issoc ia t ing i n t o monomeric complexes.36 The mechanism o f the reduction of ketones t o =-alcohols by anionic carbonyl complexes of C r , Mo and W under high hydrogen pressure has been i n ~ e s t i g a t e d . ~ ’ Cat ion ic i r i d i u m hydrides e . ~ . [IrH2(PEt2Ph),]+, catalyses the se lect ive reduction of U, $-unsaturated carbonyl compounds t o unsaturated alcohols. Chi ra l 1 igands

gave modest op t ica l y i e l d s (eq.4).38 macrocyclic Co Schiff-base complexes the formation of a metal hydride i s the r a t e determining step. The react ion fo l lows 2nd order k i n e t i ~ s . ~ g Ketones can a lso be reduced by BH4- i n a i r i n the presence of Rh porphyrinato complexes;

Imines are reduced to amines by Rh complexes i n alcohol solvents under 1 bar H,; cat ion ic complexes are the most a ~ t i v e . ~ 1 Mo-S complexes, e . ~ . (31, reduce azobenzene t o diphenylhydrazine and nitrobenzene f i r s t t o PhNHOH and f i n a l l y t o a n i l i n e under mi ld condition^.^* The i r o n t h i o l a t o complex (4 )

achieves a s imi la r reduction of ArN02 t o ArNHOH; electron-wf thdrawing

subst i tuents on the aromatic r i n g accelerate the reac t i0n .~3 A series of Ru

and 0s complexes e.g. FMX(CO)(PPh3)3 ( X = C1,Rr % . I , have been compared f o r the reduction of nitrobenzene t o a n i l i n e by H 2 or CO; CO/H$ i n the presence o f KOH and a Ru c a t a l y s t i n po lar solvents gave the best resul ts , whi le 0s complexes are poor catalysts.44 RuC1 2(PPh3) i n conjunction w i th pal ladium on charcoal i s su i tab le f o r the se lect ive reduction of a var ie ty of funct ional groups by Et3NH+02CH’ (Scheme 11.45 Polymer attached catalysts, e.~. Rh on poly(vinylpyrrolidinone), are h igh ly ac t i ve i n the hydrogenation of aromatics

and sugars ( t o sugar alcohols) and approach the a c t i v i t y of slow enzymes.46

pressure. product.

developed.

The spec i f i c hydrogenation

Diphenylacetylene gives

Ruthenium and osmium hydrido complexes, e . ~ . RuH(C0) (PPh,) o r

I n the reduction of benzi l catalysed by

again, metal-hydride formation determines the rate.40

-

Alky l isocyanates are reduc t ive ly dimerised by [H,RU,(CO)~,]’ a t 50 bar H,

Phenyl isocyanate gives only diphenylurea as a decarbonylation The Ru c l u s t e r can be recovered unchanged.4’

Increasingly, a1 te rna t ives to hydrogen as reducing agent are being Without exception pal ladium phosphine complexes are used as


Pd(0) - D Z O O M c N H 4OOC H

Ph AooR NHCOMe

( 7 )

+& 0 Ph

1 I H Ph2P PPh2

(9)

(11)

COOBU' , etc. R = H , CHZPh, Me, CHO,

Me

6 6 " I a

bPPh2 \

PPh2 ( 8 1

h2 OQoM

oxo

Me (OCH *CH *),.-OC H C H

'0 H

(13)

E = P, AS

(14)

Homogeneous Catalysis by Transition-metal Complexes 39 1

cata lysts . Thus, Bu3SnH reduces various dichloropropenes to 6- and

- Z-l-chl oroprop-l-ene48 and 1,1, ls4-tetrachl orobut-2-ene to

1, l - d i c h l orobutadiene, while rad ica l -type reductions give d i f f e r e n t products.49 Bu3SnH a lso reduces a1 l y l i c esters and gives a-bromoketones i n the presence of N-bromosuccinimide (eq.5) .So Ally1 carbamates are s i m i l a r l y reduced to primary mines; the method i s appl icable to the &protect ion of aminoacids.51

Potassium formate reduces l-chloromethylnaphthalene to methylnaphthalene

i n a C,H,/H# two-phase system using crown-ether funct ional ised phosphines as ligands, e . ~ . (51.52 L inear polyether phosphines and water soluble sulfonated phosphines are also ac t ive i n the reverse t ranspor tat ion of organic substrates i n t o the aqueous phase where formate reduces a l l y 1 hal ides t o 01 e f i ns .53 Aryl f 1 uoroal k y l s u l f onates are reduced to arenes using a Bu3N/HCOOH/DMF/Pd(PPh3)4 system.54 Aryl t r i f l a t e s are reduced by a s i m i l a r system using 1,l I - b i s (diphenyl phosphi nolferrocene as 1 i gand.55 A1 l y l i c acetates are c leanly reduced to terminal o l e f i n s using a Pd2(dba)~Bu,/HCOOH/NEt, mixture (eq.61.56 The same ca ta lys t hydrogenolyses

epoxides stereospecif i c a l l y 5 7 and reduces a1 kynyl carbonates t o 1,Z-dienes (eq.7).58 A less common reducing agent, SmI,, also reduces alkynyl

carboxylates to 1,2-dienes i n the presence of a secondary alcohol as solvent.59 The product s e l e c t i v i t y of the reduction of a l ly l i c -su l fones

w i t h LiBHEt3 i s s t rongly substituent-dependent; the synthesis of co-enzyme Q ~ o . ~ o

the react ion was applied t o

3 Asymnetric Hydrogenations

The enant ioselect ive reduction of dehydroaminoacids has continued t o

a t t r a c t a t tent ion. Rhodium cata lysts w i th a number of c h i r a l l igands have been used. Ligand (6) gives up to 70% enantiomeric excess and 100%

conversion.61 Chelat ing phosphinites derived from a series of c h i r a l aminoalcohols achieve up to 86% x., the reduction of prochi ra l ketones i s less s ~ e c f f i c . ~ 2 ~ ~ 3 The reduction of (7 ) (R = H) can be car r ied out w i th formic acid and (-1-norphos (8) i n up to 67% e,e.,64 o r w i th phosphinites of

carbohydrates, 2. (91, and H, i n 94-99% e 2 . catalysts.65 These ca t ion ic ca ta lys ts remain h igh ly ac t i ve when attached t o ion-exchange resins.66 Another carbohydrate der ivat ive, (101, helps to convert d imethy l i taconate to dimethylmethyl succinate i n 100% e.e.67 A large number of llpyrphosll der ivat ives (11) has been employed to reduce (7) w i t h usual ly high op t ica l p u r i t y under 1-70 bar H2.68 Related d ica t ion ic complexes, e . ~ . (121, achieve t h i s reduction i n methanol and water w i th high sel e c t i v i ty.69 Other 1 igands employed are 1,2-bi s ( d i phenyl phosphino)-

Neutral complexes are poor


(15) (16) (17)

R'-C-C-NH-CH-COOM~ ___) R'-EH-C-NHCH-COOMe I I I I OH 0 R2 (Eq. 8 )

I R2

II II 0 0

R = OMe

Yo Ph

Pd ____)

25 O C

R " W - C O R ' I (Eq. 8a)

99'1. e.e.

H I

MeS-C H2CH2-k-COOH A NHAc

II 0


cyclobutane70 and the P and As l igands (13); - N-acetyl-(S)- leucine from i t s dehydro-precursor i n 94% E. l igands are superior t o P.71 Sulfonated c h i r a l phosphines al low the reduction of (7) t o be car r ied out i n an aqueous/organic two-phase system.

Higher H2 pressures are ad~antageous.~2 P r o t i c media can also be used w i th polyether ligands, e.~. (141, though the e.e. i n water i s only 30%.73 Numerous l igands have been tested f o r the reduction of (L)-a-E-acetyl ami nocrotoni c aci d derivatives; (8) gives 91% e.e.74 Rhodi um

complexes derived from (11) and attached t o s i l i c a achieve up t o 100% opt ica l purity.75 The reduction of (15) i s achieved by PdC1, and H 2 i n the presence

of (2)- ( - )-a-phenylethyl ami ne .76 The s te reose lec t iv i t y of the hydrogenation of c h i r a l unsaturated esters

e.g. (16) i s determined by the conf igurat ion of the ester when complexed t o Rh, even i f no c h i r a l l i gand i s present; the two enantiomers react w i th

s i g n i f i c a n t l y d i f f e r e n t r a t e ~ . ~ 7 The c y c l i c ketone (17) i s reduced i n up t o 91% e., under 50 bar H2 using cyclohexylphosphine analogues of (111.78 The

cyclohexyl phosphines ( + I - and ( - ) - (18) reduce l - (a-ketoacy l )-a-amino esters se lec t ive ly under smooth condi t ions (eq.81.79 Rh cata lysts , =. [Rh{(S,S)-diop)Cl 12, give s i g n i f i c a n t d iastewmer ic excess i n the reduction of dehydropeptides; a s y m t r i c induction.80 A rare example f o r Ru as asymnetric hydrogenation c a t a l y s t i s the quant i ta t i ve reduction of a l k y l idene tetrahydroisoquinol ines

w i t h (binap)Ru(OAc)2 i n over 99% s. under 4 bar H2.81 (eq.8a).

the l a t t e r gives I n some cases As

-

the asymnetric substrate i t s e l f gives no or only modest

4 Hydrogen Transfer Reactions

Ruthenium hydride complexes catalyse the reduction of diphenylacetylene t o c is -s t i lbene and dibenzyl using methanol as H-source. The ox idat ion product

i s methyl formate or, i f NH4+ i s present, hexamethylenetetraamine. The a c t i v i t y decreases i n the order H2RuL4 - H2Ru(C0)L3 > HRuC1L3 > RuC12L2 > HRhL4 (L = PPh3).82 The reduction of acetophenone and aromatic aldehydes by [Rh(nbd)L 2]+/NaOPrf i n Pr fOH decreases w i th decreasing e lect ron donor a b i l i t y of L or e lect ron r ichness of the a l d e h ~ d e . ~ 3 The photo ly t i c dehydrogenation of isopropanol t o give acetone and H2 i s catalysed by - cis-[RhCl(CO)(dppm) l 2 i n the presence of acetone as photosensitizer.84

asymnetric reduction of pmethylacetophenone by Pr iOH; 75% g.e-. a t 31% conversion were achieved.85 2,2 ' -b ipyr idy l l igands carry ing asymnetric subst i tuents i n the 2-pos i t ion are less se lec t ive i n the reduction of acetophenone and give t y p i c a l l y 2-5% opt ica l yield.86 Bet te r resu l ts are achieved w i th I r (cod) lacac ) and menthyl phosphine 1 igands .87

Rh complexes of the c h i r a l l igand (19) i n the presence of KOH catalyse the


New intermediate complexes, e 3 . (201, were iso la ted from the

polymerisation of PhSiH, t o give poly(phenylsi lane1 and H2 i n the presence of Cp,TiMe, as catalyst.88

5 Isomerisations and Rearrangements

1,5-Cyclooctadiene isomerised t o 1,3- and 1,rl-cod by Cp2TiC1 ,/PriMgBr.

The react ion i s suppressed by pyr id ine and blocked by p r o t i c or ch lor inated solvents.89 The same c a t a l y s t isomerises and cyc l ises 1,5-hexadiene t o mainly 2,4-hexadiene and l-methylcyclopentene; the s e l e c t i v i t y i s determined by the T i : o l e f i n rat io.90 The complexes (arene)NiR2 (R = SiC1, > SiF, >C6F5)

are h igh ly ac t i ve f o r the isomerisation of l - b ~ t e n e . ~ l The ca t ion ic Ru hydride (21) r a p i d l y isomerises l-hexene and l-octene i n t o 2- and 3-alkenes a t

25OC. This new ca ta lys t i s a lso ac t ive i n the dimerisation of ethylene and the polymerisation of methyl acry la te and isoprene, but not of butadiene.92 A f t e r incubation w i th H,, [Ir(cod)(PPh,),]PF, isomerises

4-tr imethyl s i ly lnon- l -ene reg iose lec t ive ly t o 4-trimethylsilylnon-2-ene; and Rh ca ta lys ts are less selective.93 The c lus te rs Os3(CO) gL( p-SPrn) have some l i m i t e d a c t i v i t y f o r the isomerisation of pentene (L = MeCN > C,H, > PPh, > C2H2).94 The isomerisation of methyl l i n o l e a t e i n the presence of RU,(CO)~, i s accompanied by H-transfer from the Pr iOH solvent t o give methyl

oleate.

2,s-disubsti tuted furans a t 1OOOC i n moderate yields.96 RuH,(dmpe), slowly catalyses the rearrangement of 2,6-dimethylphenylisocyanide t o indole a t

14OOC. The suggested mechanism involves C-H ac t i va t ion of the aromatic methyl groups.97 The ring-opening of epoxides i s catalysed by NiRr2(PPh,)2; N i (0 )

o r more basic l igands are less e f f e ~ t i v e . ~ 8 Lab i le Pd(I1) complexes, e.~. PdCl 2(NCPh)2, are ac t ive ca ta lys ts f o r the Claison rearrangement of a l l y l thionobenzoate to a l l y l thiolobenzoate (eq.9).99 Ally1 v iny l ethers are s i m i l a r l y rearranged t o ketones provided tha t a l k y l subst i tuents of the v iny l

group prevent i r r e v e r s i b l e complexation to the metal . loo The asymnetric

a l l y l rearrangement of (22) i s achieved i n >70% s. by a Pd(O)/diop ca ta lys t

a t ooc (eq.10).101 Radical mechanisms are invoked w i t h the help of l a b e l l i n g experiments i n

the Co catalysed 1 somerisation of bicyclocyclobutane carboni t r i l e t o cyanocyclobutene.lo2

Ru

Rub, Fe, and Os3 c lus ters are less active.95

Pal ladium(0) complexes catalyse the c y c l i s a t i o n of acety len ic ketones to

6 Hydros i l y la t ions

Using polymethyl hydrosiloxane as H-donor, a RhCl ,/A1 iquat-336


&, + HSiR3

Pr \ /

H---C - C H2 0 PP h 2

MeNH COOR

L-Ni-Et

CN I

Me

% + DCN ZnCl2, Ni [P(OPhI3l4 MeCN 3 + : H (Eq.12) D D CN

Nu = CH(COOEt), , NMePh

Scheme 2


(= MeN(octyl1 3+Cl-) c a t a l y t i c two-phase system reduces alkynes t o (mainly)

- c i s-ol e f ins, benzoylchloride t o benzal dehyde and cyc l ohexenone t o cyc l ohexanone under very mi ld ~ o n d i t i o n s . 1 ~ 3 The regio- and s te reose lec t iv i t y of the

reduction of a series of a, $-unsaturated carbonyl compounds w i th Ph,SiH, i n the presence of Pd(PPh,), and ZnC1, has been i n ~ e s t i g a t e d . 1 ~ ~ The ac t ive form of Speier 's ca ta lys t (H,PtCl 6 ) i n the presence of dimethylvinylsi loxane has been

i d e n t i f i e d as a Pt (0) species which contains coordinated s i l y l v i n y l groups.105 On the other hand, c o l l o i d a l P t was shown t o be present i n H2PtC16 so lut ions i n Pr iOH, and very small metal p a r t i c l e s (6-60 A diameter) form when (cod)PtC12 reacts w i th HSi(OEtl3. These co l lo ids are more ac t ive hydros i l y la t ion ca ta lys ts than (codIPtC1

obtained by t r e a t i n g S-containing polysi loxane on 90 , w i th H,PtCl ,.Io7 The hydros i l y la t ion of 1-hexene w i th HS iE t , i n the presence of I r ( I 1 complexes

gives mainly unsaturated hexenylsilanes. ligand-dependent.108 109 A number of Rh complexes of long-chain si lyloxyphosphine l igands have been prepared which catalyse the react ion of 1-hexene w i th HS i (OEt) ,.I10 Rh diazadiene complexes catalyse the

hydros i l y la t ion of i n te rna l and terminal alkynes; the alkyne subst i tuents determine the reg iose lec t iv i ty.111

s i l y l ated enami nes from subst i tu ted azadienesl lz and hydros i l y l a te isoprene t o give mainly (231, whi le RuHCl(cod)(diazadiene) i s se lect ive f o r (241, with

(25) and (26) as minor by-products (eq.l l ).l13 Quinones are hydros i ly la ted by RhCl (PPh,) t o give, successively, hydroquinone mono- and d i s i l y l e ther ,114

complexes (L* = (271, (281) i n up t o 43% e.e. a t 200C.11~ Rh complexes of diazadienes carry ing menthyl subst i tuents achieve op t ica l y i e l d s of up t o 36.5% f o r the same reaction.l16 The hydros i l y la t ion of Ph(Me)C=NOH w i t h H,SiPh, gives up t o 23% =. w i t h a Rh/(-1-diop catalyst.117 The X-ray s t ructure o f the a c h i r a l Rh c a t a l y s t precursor (29) has been determined.118

i t s e l f . lo6 Supported cata lysts fo r the hydros i l y la t ion of acetylene w i t h HSiMeCl are

The product composition i s

Closely re la ted ca ta lys ts produce mainly

The asymnetric hydros i l y la t ion of acetophenone i s induced by Rh(L*) ,

7 Addi t ion Reactions t o C=C and CS Ronds

The mechanism of the hydrocyanation of ethylene and butadiene has been the subject of a b r i e f review. The equ i l ib r ium concentrat ion of one c a t a l y t i c intermediate, HNi(CN)L,, i s s t rongly dependent on the s t e r i c demand of L.119 The mechanism of the hydrocyanation of ethylene has been invest igated i n de ta i l by NMR. A productive and a non-productive cyc le ex is t , and an intermediate, (301, has been characterfsed a t -4OOC.120 The addi t ion of K N t o

BUtCH=CHD, gives >90% erythro-(311 (eq.121, whi le cyclohexadiene gives both


yo M e 3 P NHPh

RYo7tR' 0

NaHC03, HMPT Pd(OAd2/Bu4N+CL- i ThpO COOMe +J - Po

I Ar Ar

Scheme 3

R'> RO-CO

Ii 0

___.) PdLn, R~LN, /

Nu-

tRu1

HOAc

R O C 0

bl R ' = M e , E t , R =H,Me,Pent

Scheme b

Pd or NI,

r.f. At-CGC-R + Me3SiCN

N C N (SiMe3)2 H

R = H , A r

l+ P h

Ph3P

( 3 5 ) , n 1 - 3


1,2- and 1,4-addition products.121

extensively reviewed.122 The addition of Et3NHtI- t o the Pd/PPh3 ca ta lys t prevents the dimerisation of butadiene during the reaction w i t h diethylamine; the product is diethylbut-2-enyla1nlne.12~ The reaction sequence of scheme 2 includes the add i t ion of nucleophiles to a 2-vinylbenzofuran and i n e f fec t introduces functional groups i n t o an a l l y l i c methyl group.124. Stoichiometric amounts of CuC1, i n a HOAc/NaOAc buffer i n the presence of a Pd ca ta lys t chlorinates and acetoxylates olefins a t elevated temperatures.125 Mechanistic studies of the telomerisation of butadiene and acetic acid using C,D6 Suggest binuclear Pd complexes as intermediates,l26 while a monomeric intermediate (32) of the reaction of butadiene w i t h alcohols has been synthesised i n a stoichiometric r e a ~ t i 0 n . l ~ ~

and PCy3 proceeds ca ta ly t ica l ly if the isocyanate is added very slowly and continuously; the product i s (33).128 [CpFe(CO) ,I2 catalyses the addition of CCl, t o terminal olefins i n the dark Ru(I1) complexes of chiral- phosphines add arenesulfonyl chlorides to styrene i n 22-40% =.I30 Perfluoroalkyl iodides add smoothly to terminal olefins and acetylenes i n the presence of Pd(PPh3) , a t room temperature.131 Aryl iodides have been added t o activated o le f ins i n the synthesis of furanones (scheme 3).132

The addition of carboxylic acids t o terminal acetylenes is catalysed by a Ru(C,Hll),/PR3/maleic anhydride m i x t u r e and gives (34) as the main product.133 T h i s stereochemistry has been exploited i n the synthesis of vinyl acetate es te rs (scheme 41.134 Mixtures of 1- and 2-en01 es te rs resu l t from PhCECH and RCOOH i n the presence of RuCl or Ru(I1) phosphine complexes.135

Sn2Me6 undergoes cis-addition w i t h terminal alkynes i n the presence of Pd(PPh3),.136 Substituted pyrroles are formed i n high yields by adding Me3SiCN to alkynes i n the presence of PdC1, or NiC12/Bui2A1H (eq.131.137 More conventionally, the Pd catalysed addition of Me,SiCN t o allenes gives l-cyano-2-silyl-2-al kenes. 138

The ca ta ly t ic amination and aminomethylation of olef ins has been

The reaction of styrene and phenylisocyanate i n the presence of Ni(cod),

a non-radical process.129

8 Alkene Dimerisations and 01 igomerisations

A very comprehensive review deals w i t h the ca ta ly t ic dimerisation of ethylene and pr0pene.13~ The Shell Higher Olef i n (ethylene 01 igomerisation) Process has been reviewed briefly.140 The cationic N i complexes (35) tr imerise propene mainly t o hexenes and methylpentenes.141 Olef i n oligomerisation ca ta lys t s , 9 (36) and (371, cyclise 1,5-hexadiene, mainly to methylenecyclopentane (c.f. ref .90).142 (37) Also dimerises l-butene to 2-,


(39) E = COOMe

( E = COOMe)

90 : 10

Ph

Ph Ph

Scheme 5 COOMe COOMe


3- and 4-octenes.143 Dimers and trfmers of ethylene are produced i n the presence of [(allyl)NiL2]+ ca ta lys t s ( L = phosphite, SbPh,, 1/2 cod1.144 Ni(0) complexes of cyclic phospholidines, (3 (38)) dimerise butadiene mainly t o 1 , 3 , 6 - 0 c t a t r i e n e . l ~ ~

The dimerfsation of methyl methacrylate and the codimerisation w i t h methyl acrylate i n the presence of a ca ta lys t derived from PdCl 2(NCPh) + 3AgBF4 is l ike ly to involve n-ally1 Pd(1V) hydride intermediates. If the dimerisation is carried out under D,, deuterium i s incorporated i n the product.146 The dimerisation of methacrylate by Ru ca ta lys t s gives a mixture of products (eq.14). The structure of one Ru complex formed i n this reaction (39) has been d e t e r ~ i n e d . 1 4 ~ Treatment of ( ~ ~ ~ ~ ) ~ u ( m a l e i c anhydride) w i t h two equivalents NaC1,H8 gives a superior methacrylate dimerisation ca ta lys t whose ac t iv i ty is increased i n polar s 0 1 v e n t s . l ~ ~

the presence of RhCl (PPh , ) t o give l inear and branched dienoic acids.149 Allenes react similarly w i t h (40) t o give mainly l inear unsaturated acids (eq.15) .15* The analogous reaction of methylenecyclopropanes proceeds under ring-0pening.1~1 The l inear codimerisation of terminal alkynes w i t h 1,3-dienes is catalysed by (cyclooctatriene)Ru(cod) .I52

The reaction of phenylisocyanate and ethylene i n the presence of a N i ( O ) / L ca ta lys t gives carboxylic an i l ides and is dependent on L and the ethylene pressure.153 The cyclodimerisation of a1 kyl styryl ketones i s catalysed by Fe carbonyls. Complex (41) can be isolated (scheme 51.154 The intramolecular cycloaddition of ally1 alkynyl amines is catalysed by Pd Schiff-base complexes and gives pyrrole derivatives.155 The N i catalysed intramolecular [4+4] cycloaddition of dienes can be up t o 99% stereoselective (eq.16). The product composition is subject to ligand-control.156 TiC14/EtA1C1 bis(trimethylsily1 )acetylene t o norhornadiene (scheme 61.157 The Pd catalysed cycl oaddi t ion of trimethylenemethanes to a, p-unsaturated carbonyl compounds proceeds w i t h very high diastereoselectivity.158 Asymnetric Diels-Alder additions are catalysed by chiral T i alkoxides; up t o 91% c. can be achieved (eq.171.159

Conjugated dienes are co-dimerised w i t h 3-alkenoic acids (9 (40)) i n

reagents catalyse the cyclo-addition of

9 Alkyne 01 igomerisations

While Ni(cod) i n hydrocarbon solvents trimerises diphenylacetylene, THF slows the reaction down and allows the interception of intermediates including the nickel acycle L2NiC4Ph4.160 The complex L,NiH(BH,) or ca ta lys t s prepared i n situ from N i ( I I ) , L and NaRH, ( L = PCy3) are highly active i n the cyclotrimerisation of MeOCH,CXCH20Me. Substrate purity is of prime


+ RC-CR r x TICLA

R = S i M q

Scheme 6

R 92 : 8

195 O C /2h Ni(PEt3)4 1 Ph

Ph R‘ R’ ’Ph

77 */* 1 lo/.

R = rncsityl , R’= %Me3

+ 1


importance.161 The mechanism of the Reppe cyclotetramerisation of acetylene by Ni complexes has been re-investigated using H13CXH; thought to proceed stepwise. formation.162 N i (azadiene) complexes cyclotetramerise propargylic alcohols t o cyclooctatetraenes i n 98% se lec t iv i ty and remain active a f t e r l o 4 turnovers.163 T h i s tetramerisation can a1 so be achieved w i t h nickel diazadiene complexes and gives 1,3,5,7-C8H,(CH20H) ,.I64 Silylated a1 kynes dimerise under the influence of N i ( P E t 3 I 4 a t 195OC (eq.181.165 The cotrimerisation of alkynes w i t h nitriles to pyridines has now been achieved by co-condensing the substrates w i t h Co atoms.166

the reaction is The presence of phosphines leads to arene

10 Alkene Polymerisations

Ethylene is polymerised by a Cr(OBut),/AlEt2Cl/MX, ca ta lys t a t 1 bar; the ac t iv i ty decreases f o r MXn = MgC1 >> CoCl2 > AlCl > NbCl The Cp2Mc1 2/AlR3 ( M = Ti ,Zr) catalysed homogeneous-phase ethylene polymerisation is l ikely t o proceed cationic intermediates. The cationic Zr complex (42) has been s t ruc tura l ly characterised; i n the absence of aluminium alkyls.168 a-Methylstyrene is polymerised by [Eu(NCMe) 3(BF4) 3]x; the molecular weight is increased a t low temperature. The ca ta lys t i s also active i n the ring-opening of quadricyclane and olefin isomerisations.169 The ethylene polymerisation kinetics of T i (CH2Ph)4 /T iBr , and T i (CH2Ph) ,/A1Br3 ca ta lys t s are nearly identical The findings support the monometallic nature of the active centre i n these ~ys tems.1~0 A ca ta lys t derived from Co(acac) */A1Et2C1 polymerises 2,3-dimethylbutadiene to a polymer w i t h 81% l,4-* and 19% 1,2-structure.l71 and Ni/dfene ratios on the polymerisation of 1, fbutad iene w i t h a N i naphthenate/BF3.0Et2/AlEt3 ca ta lys t has been studied. The product is 1 , 4 - * - p o l y b ~ t a d i e n e . ~ ~ ~ During the butadiene polymerf sation w i t h V(mesity1 l3.THF, V-C *bonds are homolytically cleaved w i t h formation of V(I1). [Ni(CNBut),](ClO,) asymnetric polymerisation of isocyanides. The products have he1 i x structures and show optical y ie lds of 7-61%.174

i t polymerises ethylene a t room temperature

The influence of the A 1 / N i , B /Al

The result ing polymer has a mixed structure.173 i n the presence of chiral primary amines catalyses the

11 Alkene Metathesis

A book on olefin metathesis and the ring-opening polymerisation of cycloolefins has appeared.175 Collections of the papers given a t the 6th International Symposium on Olef i n M e t a t h e s i ~ 1 ~ ~ and a t the 5th International Symposium on Ring-Opening Polymeri sation177 have been published.

Homogeneous Catalysis by Transit ion-metal Complexes 403

( 4 3 ) R, = CMe(CF3)* : R = 2.6 - Pri2C6H3; R’ = SiMe3

R

WCI6/SnMe4

-15 OC

(46)

Scheme 7

Scheme a

40 O C

- ‘6 H6

C14W=NR + R’N=C=NR’ C l W H N P N R ’ ‘N

R’

R’N=C=NR + CI,W=NR’

Scheme 9


The well-characterised W complex (43) is highly active f o r the metathesis of e - b u t - 2 - e n e i n the absence of a Lewis acid and produces an equilibrium mixture of o le f ins a t g. 1000 turnovers per minute a t 25OC. vinyltrimethylsilane t o give a metallacycle whose structure was determined (eq.19).178 The metathesis ac t iv i ty of a ser ies of complexes WC1,(0-2,6-X2C6H,), activated by m a i n group IV alkyls increases f o r X = Me < Ph < F< C1 < Br and SnMer, < SnB,n < PbBu,,n, Complexes w i t h X = C1, Rr i n the presence of SnR, a re best suited f o r the metathesis of o le f in ic e ~ t e r s . 1 ’ ~ The ca ta ly t ic ac t iv i ty of W ( C H B U ~ ) ( O C H ~ B U ~ ) ~ B ~ ~ - ~ I n = 1,2,3) increases greatly on addition of G a b 3 because of the formation of cationic alkylidene complexes.180 The ring-opening polymerisation of cyclooctatetraene by W[OCH(CH2C1) JnCI 6,n/AlEt$1 i s reversible.181

presence of SnMe,.182 A WOCl ,/2MeLi reagent l ibera tes CHI, and presumably generates W = C H 2 complexes which metathesize l-he~adecene.1~3 M o ( N O ) ~ L ~ C ~ ~ ( L = pyridine, PPh, , PhCN etc.) can be attached t o an OH containing polymer. On activation w i t h A1Et2C1 i t gives the same ac t iv i ty as a homogeneous a n a 1 0 g u e . l ~ ~ Mo and W ca ta lys t s suitable for the metathesis of propene are generated by depositing M(diene1, complexes on SiO, or A l 2 O , supports.185

complex (44) as ca ta lys t . =-coordination of the olefin is necessary f o r ca ta ly t ic ac t iv i ty . The performance is improved by irradiation, by the solvent and especially by Lewis acids.lS6 A w(co)6/cc1, mixture becomes a slow ca ta lys t for l-octene metathesis under photolytic ~ o n d i t i o n s . 1 ~ 7

gives a polymer w i t h 75% trans-double bonds. original carbyne ligand remains bound t o W during the polymer formation and continues t o exert s t e r i c control (scheme 7).lR8 Cyclopentene and a WC16/epiChlOrOhydrin/RU 3iAl ca ta lys t give a polymer w i t h trans-C=C linkages, whereas WC1 6/SnPh4 leads to C i s - C - C bonds.189 Unsaturated d ies te rs are co-metathesized w i t h cyclopentene j n the presence of WC16/SnMe, t o give a,vdifunctional 01 i g 0 m e r s . 1 ~ ~ The same ca ta lys t i n toluene polymerises cyclohexene a t low temperature. The product has a moderate molecular weight and reverts t o the monomer on warming. obtained a t 25OC.191 The addition of 1,3-cod t o the 1,5-cod substrate changes the =s-C=C content of the result ing polymer from 80 t o 15%. conjugated diene is not consumed. A WC1 ,/EtOH/EtAlCl used.192 T h i s ca ta lys t also polymerises 1,4-cod.193

large range of W catalysts was tested.194 The polymerisation of (46) gives a

I t reacts w i t h

- -

Olefins and WCi6 form WC1, which gives highly active ca ta lys t s i n the

The mechanism of norbornene polymerisation has been investigated using

The ring-opening polymerisation of cyclopentene w i t h C1 ,(DME)WzCBut A mechanism is proposed where the

Cycl ohexene-norbornene co-polymers are

The (1:1:6) ca ta lys t was

The synthesis of fluoropolymers is possible via the metathesis of (45); a


c p 2Tix Ph Ph

co + -c02

M cC =C - S i Me2-( CH2)n- S i M c3

hv ___)

-H2

r 1

L J

R3 , R2

R' ( E q . 21)

H

Scheme 10

tCo1

CO/H2 - EtCOOH + PrCOOH + (Eq. 22 )


thermally sens i t ive polymer (Mr G. 2.105) which can be converted t o polyacetylene by benzene e l im ina t ion (scheme 8) .I95 The product s t ructures of the ring-opening polymerisation of endo- and exo-dicyclopentadiene,

catalysed by the hal ides of W, Nb, Re, Ru, 0s and Ir, have been invest igated by 1 3 C NMR.196 As a model f o r polymer degradation studies, the dehydro-dimer of 1,5,9-~yclododecatriene was metathesized w i th 4-octene and 3-hexene and the products analysed by GC-MS.197 The metathetical chain scission of polybutadienes i s possible w i th a WC1 &nEt4/Et20/arene ca ta lys t and al lows the determination of the polymer ~ t r u c t u r e . 1 ~ 8 The metathesis of a lkeny ls i lanes

CH2=CH(CH2)ESiX3 w i t h 2-pentene i n the presence of a WCl, c a t a l y s t proceeds wi thout an induct ion per iod for 1 = 1, X = Me. necessary i f X = C1, OMe. a f fec ts the E/Z s tereose lec t iv i t y , poss ib ly because of the formation of

ca t ion ic carbene complexes.199 W(V1) imido complexes catalyse the metathesis of carbodiimides (scheme 9) .zoo

The addi t ion of SnMe, i s The addi t ion of A l X , increases the r e a c t i v i t y and

12 A1 kyne Polymeri sations

Smooth, compact polyacetylene f i l m s of r e l a t i v e l y high density are

produced using Ti(OBun),/R2Al-E-A1R2 ca ta lys ts (E = O,S,NBun). The cis content i s over 90%.201 Cp,MCl , / E t A l C l and metal lacycles such as (47) give oligomers and polymers of phenylacetylene. Cp2Ti(CO) i s less active.202 TaC1, alone or i n conjunction w i th SnPh, polymerises the a lkyny ls i lane (48). MoCl,/SnPh, and WC16/SnPh, do not give polymers i n t h i s case.203 A re la ted

TaCl 5/BiPh3 (1: 1) cata lys t produces poly(1-trimethylsilyl-1-propyne) wi th very high molecular weight (up t o M r = 4.10,) i n near-quanti tat ive yield.204 TaC15/SnBu,n polymerises C,F,CXR ( R = Me, Et, Run). The product i s s tab le and non-f usible.205 A new a1 kyne-a1 k y l idene complex (49) has been prepared

which induces the slow polymerisation of phenylacetylene.206 Alkyne tungsten carbonyl complexes i n alcohol sol vents are converted i n t o carbene complexes which then proceed t o polymerise a l k y n e ~ . ~ O 7 The olef i n metathesis ca ta lys t (44) also polymerises RCzCH (R = H, Ph, Pentn, But); the rates are s i g n i f i c a n t l y enhanced by Lewis acids, 3. AlEt,, REt,, R(OEt)3.208 WC1, polymerises phenylacetylene more e f f e c t i v e l y than a l k y l subst i tu ted alkynes. The mechanism i s l i k e l y t o invo lve tungsten carbene intermediates; these may be converted to carbyne species which are then able t o metathesize 01 e f i ns .209


13 Carbonylations

Rhodium and iridium complexes are able to carbonylate benzene t o Coordinatively unsaturated benzal dehyde under photolytic conditions.

intermediates such as (50) are formed above 75OC (eq.20). The reaction is, however, thermodynamically unf avourable, and the ca ta ly t ic ac t iv i ty does not exceed three turnovers

N 2 and C02.211 The mechanism of the reduction of aromatic n i t ro compounds by C O to give isocyanates has been studied by IR; the ca ta lys t i s - trans-PdC1 2(pyridine) 2.212 Fe(C0) 5, R u 3 ( C O ) 12 and Rh6(CO) 16 convert - ortho-nitrostyrenes and CO into indoles i n up to 75% se lec t iv i ty (eq.21).213 Ni12(PPh3) under CO pressure catalyses the conversion of nitrobenzene and an i l ine t o diphenylurea and CO,; solvent.214 R u 3 ( C O ) 12 catalyses the carbonylation of amines to formamides and the hydroamidation of olefins to carboxylic a m i d e ~ . ~ 1 ~

heterocycles oxidatively in to esters.216 Conjugated dienes, CO and MeOH are oxidatively turned into a l l y l i c ethers and unsaturated es te rs by a Pd(II)/Cu(II )/Aliquat-336 system. however.217 The amidocarbonylation of a l l y l i c alcohols to N-acyl-a-aminoacids has been reviewed. Co,(CO), i n the presence of a co-catalyst, e . ~ . R h H ( C O ) ( P P h 3 ) 3 , PdCl 2 ( P P h 3 ) 2 o r Fe2(CO) (scheme 10). The amidocarbonylation of epoxides requires the addition o f Lewis acids.21* The dehydration of the a l l y l i c alcohol s ta r t ing material i n t h i s reaction may lead to amino acid s i d e - p r o d u ~ t s . ~ 1 ~

160-24CPC.220 The decarbonylation of t r i c y c l i c bridgehead acid chlorides has been achieved by a PdBr2/NBu3n catalyst.221

13.1 Carbon monoxide reductions - A review deals w i t h the potential and recent developments of synthesis gas chernistry,222 and another w i t h the role of Co, Rh and Ru ca ta lys t s i n the d i rec t conversion of CO and H2 t o ethylene glycol .223 The ca ta ly t ic ac t iv i ty of a number of mixed-metal clusters, - e.g. [PtRh5(CO)15]- , i n the reduction of CO a t 1400-2000 bar has been compared w i t h mnonuclear complexes.224 Catalyst turnover numbers and s e l e c t i v i t i e s f o r ethylene glycol (and i ts derivatives) increase significantly a t higher temperatures (230-3WC) and pressures (1800-2000 bar) w i t h Rh,(CO) 12 f n N-methylpyrrol idone (NMP) as catalyst.225 Using Co2(CO) i n phenol/m-cresol (5:1), the se lec t iv i ty for ethylene glycol increases greatly over methanol a t higher H 2 pressure.226 The presence of onium s a l t s improves the se lec t iv i ty

f o r ethylene glycol i n the system Ru3(CO)i2/ERb+X- (E = N,P).

Nitrous oxide is reduced by CO i n the presence of [Rh(C0)2Cl]2 and base to

the amine is used as the

Pd(I1) ca ta lys t s i n the presence of of Hg(I1) s a l t s and alcohols convert

Conversions and s e l e c t i v i t i e s are moderate,

The reaction is catalysed by

Formic es te rs are slowly decarbonylated to alcohols by IrC1(CO)(PPh3), a t

[(Ph3P)2N]+


favours the glycol formation, as does the ha l ide i n the order I-< Br-< Cl.227 The glycol formation is also promoted by 1- and 4-methylimidazole i n a R u 3 ( C O ) 12/CsI ca ta ly t ic system.228 Tertiary ammonium cations promote the generation of ethylene glycol i n the presence of Rh4(CO)12. Quaternary amnonium cations have no effect.229 Good ethylene glycol s e l e c t i v i t i e s are achieved w i t h a Rh ca ta lys t i n the presence of PR3 ( R = P r n , Bun) i n very large excess. The solvent i s 1,3-dimethyl-2-imidazolidinone.230 The formation of ethylene glycol i s strongly influenced by the electronic and s t e r i c parameters of bulky phosphines, i& PBunBut2 > PBut , > PBun2But > PBun3. The dimer [ R h ( C O ) 3 ( P P r 3 i ) ] 2 was isolated from a P P r i 3 containing reaction mixture.231 by a second research group. decompose to give Rh phosphido c lus te rs which inh ib i t the catalysis.232

hydrido species which generate formaldehyde and methanol on irradiation.233 Ruthenium ca ta lys t s i n sulfolane convert CO, H2 and NH, i n t o H2NCH0, MeNHCHO and Me2NCH0 a t 2300C and up to 340 bar pressure. Methanol formation i s not involved.234 H20s(C0),, can be heterogenised on basic MgO; the result ing ca ta lys t reduces CO to methane and hydrocarbons.235 CO and CO, can be reduced electrochemically t o methanol from a solution containing Na3[Fe(CN)5(H20)]/KC1. The current my be supplied by a solar ce11.236

13.2 Water-gas shift .- R u 3 ( C O ) 12 and 2,2’-bipyridyl produce a highly active ca ta lys t f o r the water-gas s h i f t reaction under mild conditions i n water.237 Metal combinations, e.g. Fe/Ru, exert a synergistic e f fec t . Rh ca ta lys t s are most ef fec t ive a n d o t enhanced by other metals.238 Pyridine improves the ca ta ly t ic ac t iv l ty of R u 3 ( C O ) 12. Primary and secondary amines give carbamates w i t h the CO, generated.239 The mechanism of the water-aas s h i f t by [Ru(bipy),(CO)Cl ]PF, i n aqueous KOH solution involves dicatonic R u carbonyl complexes which are readily attacked by OH-. The reaction proceeds a t 70-15OOC/2-20 bar CO.240 Palladium or rhodium ca ta lys t s are used to reduce aryl azides w i t h CO and water to give aryl amines and N,. Reactions w i t h alkyl azides were not successful .241

13.3 Carbonylations and homologations of alcohols and esters. - The f i r s t example of an anionic Co acyl complex of the type postulated i n the carbonylation of methanol has been isolated from [(Ph3P),N][Co(CO),] and Me1 (51).242 A brief review sumnarises the conversion of methanol t o acetic acid over Rh/I- catalysts.243 The ac t iv i ty of similar ca ta lys t s f o r the carbonylation of methyfacetate to ace t ic anhydride has also been surveyed.244

step i n the carbonylation of methanol, I s accelerated a t low water levels by

The same phosphine e f fec t was found Phosphines and phosphites w i t h small cone-angles

Rh porphyrin complexes react w i t h CO and H 2 thermally to give formyl and

The oxidative addition of Me1 to Li[RhI,(CO),], wh ich is the rate-limiting

additives such as LiOAc > [M~CSHI,NM~]I > LiI > LfBF4.245 Synergistic e f fec ts


CO 1 bar

(53)

OAc + CO + HSiEt2Me (Eq. 24 1 0s i Et 2Me

R

R P R + ’*+ 0 CHO

R

Rkf R = aryl

CHZPPhz CH2PPhz

M e O b q O M e

M e 0 , 0 ‘OMe

P h 2PCH2 CH2 + NMe3

&Me OMe (56)

(IPh 1, ( 5 7 ) (58 )

410 Urganometallic Chemistry

i n methanol carbonylation are found between iodide promoted Rh and Ru catalysts. Excess Ru gives the highest s e l e c t i v i t i e s to ethanol. The a c t i v i t y , however, is no be t te r than w i t h Ru/Co catalysts.246 The kinetics of the carbonylation of n-propanol and n-butanol w i t h Rh/I- ca ta lys t s have been determined.247 Potentially bidentate ligands, 3. (521, have been used i n the carbonylation of methanol i n a system MeOH/Ca/I-/(52)/Ru. Product se lec t iv i ty depends on the H2/C0 r a t i 0 . 2 4 ~ Related furfuryl phosphines gave the best s e l e c t i v i t i e s i n the homologation of MeOH over Co/I' catalysts. The coordinating behaviour of these 1 igands has been studied using model compounds.249 Similar ether-phosphines a s s i s t i n the homologation of MeOH using a Co(OAc),/RhCl , / I 2 ca ta lys t a t 180OC/200 bar. t o ethanol a t over 61% conversion were a ~ h i e v e d . 2 ~ ~

In the Ru/I- catalysed homologation of methyl es te rs , four reactions were found to occur simultaneously: homologation, es te r carbonylation, acyl group reduction and e s t e r hydrogenolysis. The homologation step i s maximised w i t h LiI as promoter, whereas Me1 favours acyl reduction.251 Mixtures of RuCl , and RhC1, i n the presence of Me1 or ZnI, convert methyl acetate into ethyl acetate and ace t ic acid; The same reaction i n the absence of RuC1, gives propionic and acetic acid instead. Ruthenium alone is inactive. 252 The conversion of methyl esters into ethyl homologues is also achieved using an iodide promoted Co/Ru system. Hydrogenolysis is a s i d e - r e a ~ t i o n . 2 ~ ~ Propiolactone is converted to mainly y-butyrolactone i n the presence of a Co ca ta lys t , while Rh gives mainly hydrogenolysi s products (eq.22) .254 The addition of Lewis or protic acids gives improved s e l e c t i v i t i e s to HOAc and AcQEt i n the homologation of MeOAc catalysed by [ R u I , ( C O ) , ] - . ~ ~ ~ The homologation of acetic acid by Ru ca ta lys t s has been followed by continuous sampling of the high-pressure reaction. The i n i t i a l rapid generation of ethanol and EtOAc is followed by the formation of propionic acid. Higher acids and es te rs are subsequently detected. A homologous ser ies of alkyl iodides i s also generated.256 Se lec t iv i t ies and a c t i v i t i e s i n the carbonylation of methyl acetate to acetic anhydride decrease f o r the ca ta lys t s RhC1, > RuC13 > PdCl,.. Wi th Zn(OAc), and Me1 as promoters, up t o 92% se lec t iv i ty to ace t ic anhydride are obtained.257

The silylcarbonylation of oxetane by HSIEt,Me i n the presence of Co2(CO), gives 83% (53) i n CH2C1,, but 96% (54) if n-hexane is the solvent (eq.23).258 The Co2(CO) catalysed carbonylative hydrosilylation of sec-alkyl acetates gives enol s i l y l ethers and has wide synthetic applications. (eq.24). Of the tert-a1 kyl acetates, only bridgehead derivatives react.

13.4 Hydroformylations. - A review deals w i t h the mechanism of the Co and Rh catalysed olef i n hydroformylation.260 The kinetics of the reaction of

IJp to 61.8% se lec t iv i ty

the se lec t iv i ty f o r EtOAc reaches 94%.

The products can easily be converted into aldehydes.259


RCOCo(C0) wf t h HCo(C0) 4r both par t i c ipants of the hydroformylatfon cycle, have been measured.261 I n the Co,(CO) catalysed react ion of HCo(C0) w i t h ethy l

acrylate, a k i n e t i c a l l y (<lOOC) and a thermodynamically con t ro l led regime (>25OC) can be dist inguished. The temperature e f f e c t f s i n accordance w i th the

in f luence of temperature on the product isomer d i s t r i b u t i o n i n the hydroformylatfon of ethy l acrylate.Z62 The scfssfon of P-C bonds of aryl

phosphf nes under hydroformylatf on condit ions i s accelerated by electron-withdrawing a r y l substi tuents and retarded by o le f f ns.263 The

hydroformylat ion of styrene by ch f ra l CO, c lus te rs proceeds w i th moderate

a c t i v f t y wi thout asymnetrfc fnduction.264

l f near/branched aldehyde r a t i o i s found a t low pressures.265 The formation

o f t h i s phosphite complex and i t s r o l e i n o l e f i n fsomerfsatfon and hydroformylatfon has been studied by W/Vis, I R and 31P MMR technfques.266

The b imeta l l i c complex Cp2Zr(CH2PPh2),RhH(PPh,) has been synthesised and used

t o hydroformylate l-hexene. The products have a low n/fso r a t i o

(1.9-2.91.267 The s t ruc tu re of a re la ted complex, Cp2Zr(CH2PPh,),Rh2(p-SBut) ,(CO) ,, has been determf ned;268 the complex

hydroformylates l-hexene a t low pressure.269 The fn f luence of L, the solvent

and the a r y l substftuents has been studied i n the hydroformylatfon of a l l y 1

arenes w i t h Rh,(p-SBut),(CO),L,. IJp t o !Xi% l i n e a r aldehyde are formed w i th L = P(OMe),) i n dichloroethane.270

Ethylene and propylene are hydroformylated by Ru cata lysts , e.~. Ru(C0) ,(PPh,),, under photo lysfs condi t ions a t low pressure. The aldehyde i s

subsequently hydrogenated.271 The hydrof ormylat ion of N-heterocycles

proceeds f n the presence of [Rh(nbd)Cl ],/PR, ca ta lys ts a t 10OoC/80 bar

p r e s ~ u r e . ~ ~ Z The hydroformylat ion and hydrocarhonylation of enynes i s catalysed by Rh4(C0),,; Cg f s more react ive than C=C (eq.251.273 Rh

complexes of trehalose-derf ved c h i r a l phosphine lfgands, e.~. (551, hydroformylate styrene, but f a i l t o show e n a n t i o ~ e l e c t i v i t y . * ~ 4 Co complexes

o f the water-soluble phosphine (56) hydroformylate l-hexene i n a two-phase system or attached to an fon-exchange res in w i th reasonable a c t i v f t y , but less se lec t ive ly than fn a homogeneous organic phase.?75 A series of anionic metal c lus te rs associated w i th polymer-attached cations has been tested as hydroformylatfon ~ a t a l y s t s . 2 ~ 6 Mixed Co,(CO) 8/R~3(CO) 12 cata lys ts show consf derably enhanced ac t f vf ty f o r l-hexene hydroformylatfon compared t o

CO,(CO)~ alone. The performance i n o l e f f n hydroester i f icat ion i s also improved.277 Co2(CO) attached t o a polyphosphazene support (57 1 hydroformylates l-hexene, thouah the formation of solut ion species i s suspected due t o cleavage reactions. ca t a 1 y s t .278

I n the hydroformylat ion of l-hexene by HRh(C0) [P(OPh),I3, the highest

Co mediated P-C bond sc iss ion deactivates the


Scheme 11

PhI + CO + Pr'OH

-COOMe

+

Y O 0 " '

PhCOOH + PhCOOPr' + PhCOCOOPr' ( E q . 2 6 )

Ph

PhCH2Br + PhCECH toluenelNaOH c O 2 ( C 0 l 8

0 &Hph (Eq.271

R2 R'ql-& 0

(591

R3

COOMe

CO 5 bar Mep. R 4 (Eq. 28 1 Pd /PPh3

MeOH 99 '10 R * MkocooMe


The mechanism of ethylene hydrof ormylat ion w i t h Pt/Sn cata lysts has been investigated.279 The diphenylphosphine oxide complex (58) catalyses the hydroformylat ion of 1-hexene and even 2-hexene t o give mainly l i n e a r aldehydes and alcohols; best resu l ts were obtained from an i n - s i t u mixture of Pt(cod),, Ph,POH and dppe (1: l : l ) .

elevated temperatures and pressures; and H2 as wel l as e s t e r i f i c a t i o n reagent (scheme 11).281 The reductive carbonylat ion of methylacetate w i th CO and H, i n the presence of a CoI,/

L i I/NPh3 ca ta lys t gives nearly quant i ta t i ve amounts of acetaldehyde and acet ic ac id .282 HCo(C0 hydrof ormyl ates 2,2-dimethoxypropane t o acetaldehyde which

reacts w i th methanol to give MeCH(OMe)2 as the main product. are a1 so effective.283 Mixtures of CoCl

Co2Rh2(CO) i n the hydroformylat ion of formaldehyde i n DMF. The s e l e c t i v i t y

t o C, products i s up t o 27%,284 13.5 Carbonylations of organic hal ides. - Several repor ts deal w i th the

carbonylation2*5, 286 and "double carbonylat ion" of a r y l hal ides (eq.261,

catalysed by PdCl ,(PPh,) ,,287 Co(CO),- under photo lys is conditions288 o r by Co2(CO) 8/Ca(OH) ,/MeI.289 Asymnetric ketones are produced from a r y l ha1 ides,

Me1 and CO by a Co,(CO) 8/cetyltrimethylammonium bromide/NaOH (aqu. 1 system290 o r from benzyl hal ides and Me1 i n the presence of Fe(C0),.291 ca ta lys ts convert PhCH2Br, HCOOR and CO i n t o carboxyl ic e ~ t e r s . ? ~ 2 PhBr, RutNC, Bu3SnOMe and a Pd ca ta lys t give aromatic im inoe~ters .2~3 PhI, CO

and Ru3SnH i n the presence of a Pd complex give mainly aldehydes,294 as does the reduct ive carbonylat ion of n-C6Hl3I i n the presence of a P t catalyst.295

But-2-en01 ides (eq.27 1296 and benzodiazepines (591297 are accessible

and Pd cata lys is , respect ive ly . The carbonylat ion of ary l t h i o l s gives thioesters,298 whi le styrene s u l f i d e (phenyl t h i i r a n e ) i s desulfurised t o styrene.299 Propargyl ic carbonates, CO and a Pd ca ta lys t give 2,3-dienyl carboxylates (eq.281.300 Ortho-substi tuted aromatic azides and Rh ca ta lys ts g ive heterocycles.301 The carbonylat ion of a r y l t r i f l a t e s proceeds i n a manner analogous to a r y l ha1 ides.3O2

There i s no a c t i v i t y without Ph2POH.280

The hydroes ter i f i ca t ion of butenes i s catalysed by Ru(CO)~(PC~,) a t

methanol serves as the source f o r CO

Rhodium complexes

and Rh4(CO) 12 are superior to

Rh/I-

Co

14 C-C Coup1 i n g Reactions

Reviews describe pal ladium catalysed ary la t ions and v iny la t ions o f o l e f ins,303 new synthet ic Pd catalysed reactions304 and coup1 i n g reactions

w i t h t i n reagents.3053306

complexes. Thus, electrogenerated a l l y l t i n reagents couple w i th a l ly l

halides307 o r imidoy l chlorides,308 v iny l t i n a l k y l s and aryldiazonium

The vast ma jor i t y of C-C coupling reactions are catalysed by Pd phosphine

414 OrganometaNic Chemistry

RC=C-(CH2),COOLi + R2CH=CRLCHR4CI

R -* ( Eq. 30) Pd ( PPh3 14 + C l Z n C E C - S i M e 3

Br ‘SiMe3

> 9S0/* se lect iv i ty

OTMS

L R Z + O C O , R ~ R’

MeCN Pd(OAcI2(dppe1 I R2

Ph Ph + R3*0Ac !:zl* :& - ( E q . 3 2 )

R 2 R3

‘8 H17 0 II

Pr‘ O’i‘Ph

M e


s a l t s give aryl olef ins,309 t i n heteroaryls react w i t h ortho-iodobenzoate310 or w i t h 0rtho-bromopyridine~1~ to give heterobiaryls, and SnMe, methylates benzyl bromides.312

aryl and alkyl Grignard reagents w i t h a l k ~ l i o d i d e s . 3 1 ~ Regioselective coupling reactions w i t h a r y l i t h i u d 1 4 and l i t h i u m alkynoates (ea.291315 have been described. Zn(CH2CH2COOR) was coupled w i t h aryl h a l i d e ~ , ~ l ~ another zinc reagent reacts w i t h the (&)-isomer only of an (E)/(L) mixture of l-bromoal kenes (eq.30) .317 Alkenyl copper reagents and acyl ha1 ides give ketones.318

Prim.-alkyl boranes couple w i t h aryl iodides;319 i n the presence of CO, unsymnetric ketones result.320 Vinyl boranes react w i t h a wide range of organic halides to give substi tuted olefins3zl or 1,3-dienes of high isomeric purity;322

C1 ,C-CN325 w i t h C-nucleophiles. ally?-a-cyanocarboxylates gives a, p-unsaturated n f t r i l e ~ . ~ ~ ~ Al ly l ic carbonates and enol ethers react under decarboxylation to give a, p-unsaturated ketones (eq.311327 and form a1 ly l thioethers w i t h EtSSiMe,.328 Ally1 ace ta tes couple w i t h diphenylketene t o give 1 ,J-dienes (eq.321329 and react w i t h ROOCCH(R1ZnBr t o give unsaturated esters.330

alky1331 and aryl halides.332 Aryl and vinyl t r i f l a t e s behave l i k e halides and give b i a r y l ~ , ~ 3 3 , alkyne~334-33~ (e.g. (6013361, alkenes,334 dienes337 and dien0nes.33~ A wide rangeof phosphinates has been made from H P ( O ) ( R ) ( O R ' ) and organic electrophiles,339-342 including the synthesis of (61) i n 93% optical purity.339

The cyclisations and cycloadditions reported include the synthesis of benzof uranes from 2-halophenol s and a1 kynes ,343 the generation of y-butyrol actams from chl orof ormami des ,344 the intramolecular ri ng-cl osure t o spirocyclic amides345 and the [3+2] cycloaddition of trimethylene methane precursors to a, pinsa tura ted a1 dehydes ,346 itnines347 and activated a1 kenes ( eq .33 1.348

The asymmetric coupling of a l l y l i c halides and Grignard reagents i n the presence of chiral N i ca ta lys t s gives high optical yields,349 as does the a l ly la t ion of chfral enamines ( u p t o 100% g . 1 3 5 0 and the treatment of ally1 ace ta tes w i t h C-nucleophiles i n the presence of chiral ferrocenyl 1 igands.3511 352 Aminoacid-derived ligands (62 induce optical ac t iv i ty i n the coupl i ng of Gri gnard reagents w i t h vinyl bromide .353 The coupl i ng reactions of cis- and trans-(631 are stereocontrolled.354

The 1,l '-bis(diphenylphosphino1ferrocene ligand was used when coupl ing

a fungal pro-hormone has been synthesised i n this way.323 Nickel catalyses the coupl ing of a1 ly l i c acetates3Z4 and of

The Pd catalysed decarboxylation of

Nickel bipyridyl complexes catalyse the electrochemical coupling of


' s w P P h 2 Me

I

NMe2

RCHO + CN-CH2COOMe

25 O C [Au L"]' 1 96'10 e.e.

WH H

,COOMe

H dN 0 (Eq. 34 1

SiMe3 SiMe3

OH OH

9 5 . 4 '10 e.e.

L9'lo e.e.

I

b H

9 2 . 1 ° / o e.e.

OAc

Pd(II)/MnO2 - HoAc , r.t. a- ( E q . 36 1

> 95'/0 selectivity


Pd catalyses the decarbonylatfon of a l l y l f c es te rs to give a-methylene ketones,355 whf le H2Ru(PPh3), converts a1 l y l i c carbonates into ketones and Cf12.356 The Pd catalysed decarbonylative cross-condensation of acyl ha1 f des gf ves a , $-unsaturated ketones.357 A1 ly l methyl t h f ocarbonate i s converted to a l l y l methyl sulffde and ~0s.358 The oxidative coupling of phthalates gfves b f a r ~ l s . 3 5 ~ Dfenes and a l ly l ethers are coupled i n the presence of Fe c a t a l y ~ t s . ~ 6 0 Heterocycles are oxf datively df- and trimerf sed by RuCl 3.361 R u phosphf te complexes catalyse the ortho-a1 kylatf on of phenol .362 A1 ly l f c alcohols and primary amines give sec-allylamines f n the presence of a Pt/Sn catalyst.363 Secondary arylamines, ethylene glycol and RuCl 2(PPh,) as c a t a l y s t give indoles;364 these are a1 so accessfble v& an intramolecular cyclisatfon.365 RuH2(PPh3), catalyses the amidation of nf t r f les , a route a1 so used to produce polyamides.366 The a1 do1 condensatf on between enol ethers and aldehydes i s catalysed by Rh complexes.367 Surprf sf ngly, chi ral gold complexes are ca ta ly t ica l ly active i n the asymnetric condensation of a1 dehydes wf t h f socyani des (eq .34 1 .368

15 Oxidations

A review describes the asymnetrfc epoxidatfon of a l l y l i c alcohols,369 another the role of metalloporphyrins i n oxidation r e a c t f 0 n s . ~ 7 ~ The Tf (OPr i 1 ,, catalysed self -epoxf datf on of a1 ly l i c peroxf des proceeds v i a an i n teml ecul a r nechanf sm.371 Racemf c a1 l y l a1 coho1 s can be resol ved by asymmetric epoxidatfon (eq.351.372 A Pd(I1 )/Mn02/benzoqufnone system catalyses the oxf dative rf ng-closure of 1,Shexadienes (eq.36).373 Propenyl phenols are oxfdatfvely degraded to aryl aldehydes and MeCHO in the presence of Co Schfff-base catalysts.374 An Oppenauer-type oxidation w i t h Cp2ZrH2/cyclohexanone converts primary alcohols selectf vely into a ldehyde~.~75 Co macrocycles catalyse the oxidation of aryl hydrazones t o diazo compounds i n high y f e l d ~ . ~ 7 ~ Similar Co complexes under CO oxfdise primary amines to azo compounds.377 Arene 0s complexes i n the presence of base convert aldehydes and water slowly into carboxylfc acids and H,.378

41 8 Organometallic Chemistry

1

2

3 4

5 6

7

8 9 10 11

12 13 14 15

16 17

18 19 20 21

22 23 24 25 26 27

28 29 30 31 32 33

34 35

36 37

38

39

40

41 42

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71 D.G. Allen, S.B. Vild and D.L. Wood, Q r g m a U 1986, 5, 1009. 72 P. Alario, Y, Amrani, Y , Col leu i l le , T.P. Dang, J . Jenck, D. Morel and D.

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77 J.M. Brown, 1. Cut t ing, P.L. Evans and P . J . Maddox, Tetrahedron Let t . 1986,

78 T. Morfmto, H. Takahashi, K . F u j i i , W . Chiba and K. Achiwa, 1986,

79 K . Tani, E. Tanigawa, Y . Tatsuno and S. O t s u k a , Chem.Lett. 1986, 737. 80 S. E l -Baba , J.W. Buzil lard, J .C. Poulin and HOB. Kagan, Tetrahedron 1986, 42,

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84 S. Shinoda, A. Kobayashi, T. Aoki and Y . Sa i to , J,Wol.Catal. 1986, a, 279, 85 P. Kvintovics, B.R. James and B. Hell, 1986, 1810. 86 C. Bolteghi, G. Chelucci, G. Chessa, G. Delogu, S. Gladia l i and F. Soccol ini ,

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226 T. Masuda, K . Murata and A. Hatsuda, 1986, 1287. 227 Y . Kiso, M. Tanaka, H. Nakamura, T. Yamasaki and K . Saekl, JJkg.awOraanom%t.Chem.

228 Y. Kieo and K . Saeki, 1986, Ul, C17. 229 E. Watanabe, K. Murayama, Y . Hara, Y . Kobayashi, K . Wada and T . Onoda,

230 E. Watanabe, Y. Hara, K. Wada and T. Onoda, - L e t t , 1986, 285. 231 H. Tanaka, Y . Hara, B. Watanabe, K . Wada and T. Onoda, J.Oraanonet.Chem.

35, 135.

1986, m, 1345.

1986, 24, 3529.

1986, & 1839.

2448.

1986, 24, 3569.

LQB, 6079.

a 1986, 2, 525.

1986, 784.

m, 333.

4615.

[iQ, 2349.

1986, m, 357.

J.Chen. Soc.. Chem,Camm. 1986, 227.


1986, U, C71.

m, c75. 232 W. Tamura, K . Ishino, T. Deguchi and S. Nakamura, 1986,

233 H. W. Bosch and B. B. Wayland, J&&&J&c,. C h a L 1986, 900. 234 J.A. Marsella and G.P. Pez, J.Wnl.Catal. 1986, 35, 65. 235 H.H. Lamb and B.C. Gates, J.Am.Chem.Snc. 1986, M, 81. 236 K. Ogura and I. Yoshida, L h l A a U L 1986, U, 309. 237 T. Venalainen, T.A. Pakkanen, T.T. Pakkanen and B. Iiskola,

238 T. Venalainen, E. Iiskola, J. Pursiainen, T.A. Pakkanen and T.T. Pakkanen,

239 T. Venalainen, E. Iiskola, T.A. Pakkanen and T.T. Pakkanen, I.nal.Catal.

240 H. Ishida, K. Tanaka, M.Horimto and T. Tanaka, 7 1986, 5, 724. 241 S.C. Shim, K.B. Choi and Y.X. Yeo, -Lett. 1986, 1149. 242 M. Roper, K. Schieren and B.T. Heaton, 1986, 299, 131. 243 D. Forster and T.W. Dekleva, J.Chem.Bduc. 1986, a, 204. 244 S.W. Polichnowski, 1986, 63, 206. 245 M.A. Hurphy, B.L. Smith, G.P. Torrence and A. Aguilb, 1986,

246 J. Pursiafnen, K. Karjalainen and T.A. Pakkanen, J.Oraanomet.Chem. 1986,

247 S.B. Dake and R.V. Chaudhari, 1986, z, 119. 248 6. Lindner, H.A. Kayer and P. Wegner, C4em,Bw. 1986, U, 2616. 249 E. Lindner, C. Scheytt and P. Wegner, 1986, a, 311. 250 E. Lindner, A. Sickinger and P. Wegner, J.t.C& 1986, U, C37. 251 J. Zoeller, J.Wol.Catal. 1986, X, 117. 252 E. Drent, m . C a & 1986, X, 93. 253 G. Jenner and P. Andrianary, J.t. Chem. 1986, m, 263. 254 G. Bitsi, H. Kheradmand and G. Jenner, 1986, m, 115. 255 G. Braca, A.M. Raspolli, G. Sbrana and F. Zanni, J.Wol.Catal. 1986, 34, 183. 256 J.R.Zoeller, JJbUWd- 1986, a, 377. 257 V.A. Wamyan, S.D. Sominskii, S.D. Pirozhkov, V.L. Barsegyan, V.D. Vardanyan

258 T. Wurai, K. Furuta, S. Kato, S. Xurai and T. Sonoda, 1986,

259 If. Chatani, S. Fujii, Y. Yamasaki, S. Wurai and N. Sonoda,

260 R.L, Pruett, J.Chem.Bduc. 1986, 63, 196. 261 I. KOV~CS, F. UngavAry and L. Mark&, 1986, '5, 209. 262 F. Ungvfiry and L. Markb, 7 1986, 5, 2341. 263 R . A . Dubois and P.E. Garrou, QraancJmetaU~s 1986, 5, 466. 264 J. Collin, C. Jossart and G. Balavoine, 7 1986, 5, 203. 265 A.M. Trzeciak and J. J, Ziolkowski, I.nol.Catal. 1986, a, 213. 266 A.M. Trzeciak, J.J. Ziolkowski, S. Aygen and R. van Eldik, J.Wol.Catal. 1986,

267 R. Choukroun, A. Iraqi and D. Gervais, S.Oraanomet.Chem. 1986, u, (30. 268 R. Choukroun, D. Gervais, J. Jaud, P, Kalck and F. Senocq, 7 269 F. Senocq, C. Randrianalimanana, A. Thorez, P. Kalck, R. Choukroun and D.

270 P. Kalck, D.C. Park, P. Serein and A. Thorez, 1986, a, 349. 271 E . M . Gordon and R. Bisenberg, 1986, m, C53. 272 K. Pr6kai-Thtraf, S. Toros and B. Hell, 1986, 3l5, 231. 273 K. Doyama, T. Joh, S. Takahashi and T. Shiohara, TPtr-nn Lett. 1986,

274 J.M. Brown, S.J. Cook and R. Khan, Tetrahedron 1986, &, 5105. 275 H. K. Markiewicz and H. C. Baird, 1986, l.l.3, 95. 276 H. Marrakchi, K . Haimeur, P. Escalant, J. Lieto and J.P. Aune, Hpuv.J.Chj~~

277 M . Hidai, A. Fukuoka, Y. Koyasu and Y. Uchida, I.nol.Catal. 1986, 35, 29.

1986, 314, C49.

1986, s, 293. 1986, a, 305.

m, 257. 227

and A.L. Lapidus, Bull.bcad.Sci, VSSB, Div.Chem.Sci. , 1985, X, 2095.

z, 249. 1986, I&&, 7361.

a, 337.

1986, 5, 67.

Gervais, 1986, 3.5, 213.

a, 4497.

1986, LQ, 159.


278 R . A . Dubois, P.B. Garrou, K . D . Lavin and H . R . Allcock, 7 1986,

279 A , Scrivanti , A. Berton, L. Toniolo and C. Botteghi, 1986,

280 P, W . B . M . van Leewen, C.F . Roobeek, R . L . Wife and J.H.G. Fr i jns ,

281 A . Behr, U . Kanne and W. Keim, I.l[ol.Catal. 1986, 35, 19. 282 R.W. Wegman and D.C. Busby, 1986, 332. 283 Y. Chauvin, D. Commereuc, F. Hughes and D. Prouteau, I,nal.Catal. 1986, 34,

284 M. Harchionna and G. Longoni, I.Kol.Catal. 1986, 35, 107. 285 T. Kashimura, K . Kudo, S. Mori and B. Suglta, Chem.Lett. 1986, 851. 286 T. Kashimura, K . Kudo, S. Mori and I?. Sugita, - L e t t . 1986, 299. 287 B. Worin, A. Hirschauer, F. Hughes, D. Commereuc and Y , Chauvin,

288 T. Kashimura, K. Kudo, S. Mori and B. Sugita, -Lett. 1986, 483. 289 F. Francalanci, B. Bencini, A. Gardano, M. Vincent1 and W. Foh, -. 290 W. Mlura, F. Akase and M. Bomora, . I . C h e m . S n c . L , h ~ 1986, 241. 291 P. Laurent, G. Tanguy and H . des Abbayes, J.Chem.Soc.. C h e n L m m - 1986, 1754. 292 C. Buchan, N. Hamel, J.B. Woe11 and H. Alper, 1986,

293 W. Kosugi, T. Ogata, H . Tamura, H. Sano and T. Bigita, 1986, 1196. 294 V.P. Baillargeon and J.K. S t l l l e , J.Am.Chem.Snc. 1986, m, 452. 295 R. Takeuchi, Y. T s u j i and Y . Vatanabe, 1986, 351. 296 H. Arzoumanian and J.F. Petrignani, 1986, 22, 5979. 297 M. Mori, Y . Uozumi, M. Kimura and Y . Ban, Tetrahedron 1986, 42, 3793. 298 S. Antebi and H. A l p e r , --I. 1986, 5, 596. 299 S. Calet and H. A l p e r , Tetrahedron Let t , 1986, Z, 3573. 300 J . Tsuji , T . Sugiura and I . Hinani, 1986, 22, 731. 301 G. La Monica, G. Ardizzoia, G. Maddinelli and S. Tol la r i , 1986,

302 S. Cacchi, P.G. C i a t t i n i , E. Worera and G. Ortar, 1986,

303 H , U . ReISig, ~achr.~hem.~ech.~ab. 1986, 34, 1066. 304 J . Tsuji , Pure ~ ~ ~ 1 . ~ h e m . 1986, a, 869. 305 J.K. S t i l l e , 1986, pB, 504. 306 T . B . Witchell, -t,cbeJa 1986, rn, I . 307 J . Yoshida, H. Funahashi, H. Iwasaki and B. Kawabata, 1986,

308 M. Kosugi, M. Koshiba, A . Atoh, €I. Sano and T. Migita,

309 K . Klkukawa, H. Umekawa and T. Hatsuda, 1986, U, C44. 310 T.R. Bailey, Tetrahedron Lett . 1986, 22, 4407. 311 Y. Yamamoto, Y . Azuma and H. Hitoh, Svnthesis 1986, 564. 312 R. Sustmann, J. Lau and M. Zipp, Tetrahedron Let t , 1986, x, 5207. 313 P.L. Castle and D . A . Widdowson, 1986, 22, 6013. 314 S. Araki, M. Ohmura and Y. Butsugan, Bull.Chem.Snc.Jm 1986, W, 2019. 315 N. Yanagihara, C. Lambert, K . I r i t a n i , K . Utimoto and H. Bozaki,

316 E. Nakamura and 1. Kuwajima, Tetrahedron Lett . 1986, 22, 83. 317 B , P . Andreini, A. Carpita and R . R O S S ~ , 1986, a, 5533. 318 N. Jabr i , A. Alexakis and J.F. Bormant, Tetrahedron 1986, 42, 1369. 319 B. Hiyaura, T. Ishiyama, M. Ishikawa and A. Suzuki, W a d r n n Lett . 1986,

320 Y. Wakita, T. Yasunaga, W. Akita and M. Kojima, J . n r g a n o m e t . C a 1986, m, 321 M. Satoh, B. Miyaura and A . Suzuki, -tt. 1986, 1329, 322 B. Hiyaura, H. Satoh and A . Suzuki, Tetrahedran Lett. 1986, a, 3745. 323 B. Hiyaura, Y. Satoh, S. Hara and A. Suzuki, Bull.Chem.Soc.Jnn. 1986, Q,

5, 460,

XU, 369.

~ . ~ h e m . s n c . . Chem.Comm. 1986, 31.

275.

1986, a, 317.

hem, 1986, m, c27.

167.

s, 327.

a, 3931,

a, 4469.

1986, B, 677.

~.~m.~hem.~oc. 1986, m, 2753.

22, 6369.

C17.

2029.


324 325

326

327

328 329 330

33 1

332

333 334 335 336 337 338 339 340 34 1 342 343 344 345

346 347 348 349

350 35 1

352 353 354 355 356 357 358 359 360

36 1 362 363 364 365

366 367 368 369 370 37 1 372

T. Cuvigny and W. J u l i n , 1996, u, 393. A.C. Veronese, C. Talmell i , V . Gandolf i , B. Corain and M. Basato, LlhLWaL 1986, U, 195. I . Winami, W. Yuhara, I . Shimizu and J . T s u j i , 1986, 118. I . Mlnami, K. Takahashi, I . Shimizu, T. Kimura and J . T s u j i , Tetrahedron 1986, 42, 2971. B.W. Trost and T.S. Scanlan, -rnn a 1986, a, 4141. T. Wltsudo, W. Kadokura and Y. Watanabe, 1986, 1539. G.P. Bo ld r in i , K. Mengoli, E. Tag l i av in i , C. Trombini and A . Umani-Ronchi,

So Mabrouk, S. P e l l e g r i n i , J.C. F a l e s t , Y , Ro l l in and J . Perichon,

Y. Ro l l in , M. Troupel, D.G. Tuck and J . Perichon, 1986, 32.3, 131. J . Yamashita, Y. Inoue, T. Kondo and H. Hashimoto, Ghe&J&L 1986, 407. Q.Y. Chen and Z.Y. Yang, Tetrahedron L e t t . 1986, a, 1171. S. Cacchi, B. Worera and G. Ortar, 1986, 320. L. Castedo, A. MouriUo and L . A , Sarandeses , 1986, 22, 1523. W.J. Sco t t and J.K. S t i l l e , J.Am,Chem.Snc. 1986, J&, 3033. A. Arcadi, F. Warinel l i and S. Cacchi, 1986, U, C27. Y , Xu and J . Zhang, m S n c . - 1986, 1606. Y . Xu and Z. L i , Svnthesis 1986, 240. X. Lu and J . Zhu, Svnthesis 1986, 563. Y. Xu and 2. Li, 1986, 22, 3017. A. Arcadi and F. Mar ine l l i , Svnthesis 1986, 749. F. Henn, J. Muzart and J .P . Pete , 1986, Z, 6339. R. Grigg, V. Scridharan, P. Stevenson and T. Worakun, J.Chem.Snc,. ChPm.- 1986, 1697. B.W. Trost and S. A. King, 1986, ZZ, 5971. W. D. Jones and R.D. W . Kemmitt, ~ S K . Chem,Comm. 1986, 1201. B.W. Trost and S.M. Mignani, Tetrahedron L p t t . 1986, 22, 4137. G. Consigl io , 0. Piccolo, L. Roncet t i and F. Morandini, Tetrahedron 1986, 42, 2043. K . H l ro i , K. Suya and S. Sa to , 1986, 469. T. Hayashi, A. Yamamoto, T. Hagihara and Y . I t o , -Lett.~ 1986, ZZ, 191. T. Hayashi, A . Yamamoto and Y. I t o , a- 1986, 1090. B.K. Vriesema and R.W. Kellogg, Jbtr- 1986, a, 2049. J .C. Fiaud and L. Aribl-Zouioueche, -.. Chem.Comm. 1986, 390. J. Tsu j i , W. Nisar and I . Winami, 1986, x, 2483. I . Winami, W. Yamada and J . T s u j l , 1986, 22, 1804. 1. Kadokura, T. Witsudo and Y . Watanabe, 1986, 252. P.R. Auburn, J . Wbelan and B. Basnich, 1986, 146. A. Sh io t an i , H. I t a t a n i and T. Inagaki , J.lrIol.Catal. 1986, 34, 57. J . W . Takacs, L.G. Anderson, G.V. Madhavan, W . W . Creswell, F.L. Seely and W.F. Devroy, Q - W 1986, 5, 2395. R. Jaouhari , P. Gubnot and P. Dixneuf, 1986, 1255. L.B. L e w i s and J . F . Smith, J.Bm.Chem.Soc. 1986, 1pB, 2728. Y. T s u j i , R. Takeuchi, H. Ogawa and Y . Watanabe, 1986, 293. Y. T s u j i , K . T . Huh and Y . Vatanabe, lletrahedron 1.m- 1986, 22, 377. Y. T s u j i , K.T. Huh, Y. Yokoyama and Y. Watanabe, 1986, 1575. S . I . Hurahashi, T. Naota and B. S a i t o , J.Bm.Chem.Soc. 1986, 1pB, 7846. S. Sa to , I. Matsuda and Y. Izumi, TetrahedronLett. 1986, 211, 5517. Y. Ito, W. Sawamura and T. Hayashi, 1986, 1p8, 6404. A . Pfennlnger, Svnthesis 1986, 89. T. Mlodnicka, 1986, a, 205. W. Adam, A. Griesbeck and B. Staab, Bnaew.Chem. 1986, pB, 279. Y. Kitano, T. Watsumoto, Y. Takeda and F. Sato, J.Chem.Snc.. Chem.Camm. 1986, 1732.

1986, 22, 4223.

1986, m, 391.


373 T. Antonsson, A . Heumann and C. Moberg, m n . . C- 1966, 518, 374 R.S. Drago, B . B . Corden and C.W. Barnes, S.A1.Chen.Soc. 1986, I&&, 2453. 375 T. Nakano, T. Terada, Y . Ishii and M. Ogawa, Svnthesic 1986, 774. 376 A . Nlshinaga, S. Yamazaki and T. Hatsuura, -Lett, 1986, 505. 377 F. Benedini, M. Bal i , B. Rindone, S. Tol lari , S. Cenini, G . La Monica and

378 J . A . Cabeza, A . J. Smith, H . Adams and P.M. Hai t l i s , F. Porta, I.nol.Catal. 1986, a, 155. 1986, 1155.

16 Structures of Organometallic Compounds determined by Diffraction Methods

BY D. R. RUSSELL

- 1 Introduction

This Chapter consists of a comprehensive list of organometallic compounds whose structures have been determined by x-ray, neutron or electron diffraction methods and reported during 1986. Metals are defined as all elements except C,H,N,P,O,S, the halogens and the inert gases. Coordination complexes of arsines, stibines, [AsPh4]+ and [BPh4]- salts, and cyanides, where these are responsible for the only metal-to-carbon bonds, are excluded. Organic compounds with silicon-containing groups are not included at this reviewer's discretion. The ordering of formulae in the Main Table is based on the modified Hill system as since volume 13. Under the Structure heading the line formula is an attempt to describe the structural identity of the compound. A supplementary list of abbreviations used additional to the list at the front of this Volume is given at the end of the Main Table. Mixed metal compounds appear only once in the Main Table. The Metals Cross Reference Table can be used to locate mixed metal compounds in the Main Table which appear alphabetically under another metal.

The Main Table contains 1869 entries, an average of 1.36 structures per citation. The most frequently occurring metal is again Fe, but there is a notable rise in interest in Mo and Ru compounds over previous years. Metals appearing in more than 100 compounds are Fe(2621, Si(193), M0(172), Ru(158), Co(1441, W(129), Rh(1271, B(108), Pt(106) and Os(102). The largest monomeric species is compound number 1184 with 277 atoms, compound 1051 has 38 metal atoms.

Structures were found in 44 different journals over the period covered, but 72% were found in only six journals, each of which has over 100 citations.


427


2 Main Table --- No. Fomwla Srmmre Derails Ref.

1 AgC5H3F7N Ag{CF( CF3 1 1 ( NCMe 1 1

1

2

20 AlSi4C30H51N3P Ph.&(p-NSiMe3 )2PPhN(SiMe3)2 17.

21 AlZr2C36H50C102 18

22 AlZr2C38H5502 Et+( KCHCH2But ) 2Z r2H( Cp ) ( 2 isomers ) 18

Me+ ( fl-On2-OCCCHCH2But 1 2Z r2Cl ( Cp)

23 [M2C$l8N3 1- [M(dibenzo-18-c-6)][Al2Me6N31.Sv (M=K,Cs) 19

25 A12C14H3404 [12-c-41[AlMe3I2 21

26 M2C21H31m MeplNMe=CPhCPhQA1Me3 20

27 A12B2C8H20C1402 (AlC12 (flu-OBEt2 1 12 22

28 a2B2C16H28Br402 IfiBr~(fl-OBC8H14) 12 22

24 A12C13H31N0 Me &NBut=CHCMe 2&dMe 20

29 M2B18C8H32 23

30 A12Ti2C22H3202 { (Cp) 2Ti (fl-H) +H( fl-Cm 1 I 24

25

A l ( o5-C2BgHll 1 I o5-C2BgH9 ( H2flEt2 1 1

31 A12Ti4CqOHq6 {Cp2Ti(fl-H)@(fl-H) (YI 1 5 :n -C5H4)TiCp(fl-H) I2.Sv

Structures determined by Diffraction Methods

No.

32

33

34

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

55

56

57

58

59

Fomwla

[A13c14H2603 I-

Al 384C24H20C1506

A13SmC12H18C112

'A13U3C36H54C117 I +

4C16H2 qC14

AsC18F17

AsC19H16N

AsC19H16ND

AsC25H20N5S3

AsAuC24H19N02 AsCo2FeMOCl5HllO8S

AsCo2FeMoC16Hlq08P

AsCo3CrC14014

Asc07c2 0'2 0 AsFeSiC15H2303

AsLic2 4H3406

AsPd2C37H4 4ClN2S

AsSbC24H20S2 [awc23H3602P2 1'

Asw3c2 lH5'1 5 [ A S ~ C ~ H I ~ I I+

As2C02C20H30S3

As2c02cr3c20020

-ZCr 2FeC26H1 0'1 4

&ZFeC2 4H3006P

As2Ga2C20H48

As2Ga2C32H72

As2Ga2si 4'40H64

429

Rrf.

26

27

28

29

30

31

32

33

34

35

36

36

37

37

38

39

40

41

42

43

44

45

37

43

46

47

47

48

49

50

51

39

430

No.

64

65

66

67

68

69

70

71

72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

87

88

89

90

91

92

93

94

95

Fonnula

As2MoSi4C19H3805

As2M02C18H2204 [As2Ni10C20H6018 1 2-

As20s6C38H36N2022S

As2PtC50H4202S

As2m2C20H3604

As2Sn2C62H54N208

As2wc1 5H30Br2F607P2

AS2W2C22H1 ool 0

As2W3C27H10015

As3C5H912

As36aC54H66 [As3NigC33Hl5Ol5I2-

As4C6H1204

-4' r4C36H7204

rAs4*2C57H51N202 I'

As6M0C40H3004

As6M02C12H1 8'1 2

As7Ga5Si6C66H102 AuC5H9C1N

AUCl OH1 3C1N0

[Auc12H18 1-

AuC14H15BrP

A U C ~ ~ H ~ ~ C ~ N ~ O ~ S

[ AUCl&N20 1

A u C ~ ~ H ~ ~ N O P

[ A U C ~ O H ~ ~ N ~ O ~ 1'

[AUC21H21N3 I'

AuC26H20P

AuC32H24F5P2 [ A u C ~ ~ H ~ ~ N ~ P I 2+ AUBwc15H19N602PS


Details

233

243

233

185

Ref-

43

52

53

54

55

56

57

58

43

43

59

60

53

61

62

63

64

65

66

67

68

69

70

71

71

72

68

73

74

75

71

76

No.

96

97

98

99

100

101

102

10 3

104

105

106

107

108

109

110

111

112

113

114

115

116

117

118

119

120

121

122

123

124

125

126

127

Structures determined by Difraction Methods 43 1 Formula

AuBwc30H25N602ps AuCoFe2C32H2308P

AUCO3RUC3oH15012P

AuMoC27H2004P

3C26H1 6'1 0

A"Os3C30H18011P

Au0s4c3 2H1 Sm1 3'

Au0s6C36H15018P2 [AuOsloC25Br024 I- [~os10C43H15024Pl-

[ A ~ O ~ ~ O C ~ O O ~ ~ 12- [-3C27H1809P 1-

[AURe7C40H15021P I 2-

AURU3C46H3209P3

m2C28H28C12P2

Au2C29H28C14P2

AU2C29H28C16P2

A'2C30H30BrNP2

A'2C31H36P2

Au2C32H3404P2

A'2C36H21C12F10NP2

m2C36H35Br0P2

AU2C38H24F10P2

Au2C42H3804P2

A'2BFe4C48H31012P2

AU2B2S 2C56H76N2P2

Au2 I '8'4 4H4 0'20'4 [Au2mSi2C52H56P2 1'

99

13

100

432

No.

128

129

130

131

132

133

134

135

136

137

138

139

140

141

142

143

144

145

146

147

148

149

150

151

152

153

154

155

156

157

158


Formula SIruclun De~ails Rer.

BC20H25N202

BC22H27m [ ~ ~ 2 7 ~ 3 2 I- [ BC27H33 I- [BC27H33Pl-

BC28H32P

BC30H32P B C O C ~ ~ H ~ ~ O ~ P

[ BCrFeC18H1403 1-

BFeC12H13F203 BFeC13H903

BFeC13H20N

BFeC16H23F203

BFeCl 7H21 F2°3

BFeC18H23F203 BFeRhWC3 4H30N604

101

101

102

185 69

103

104

105

106

107

107

hcBu ( C6H4NHCMehh-~ 1 108

BF(9-fluorenyl)(Me4piperidino) 109

[Li(l2-~-4)~][B(C~H~Me~==CH~-2,6,4)Mes~].Sv 140 110

[Li(l2-~-4)~l[~~es~l & mes3 130 111

[Li(12-~-4)~][Mes~BPMesJ 130 112

l-(Ph3PCH2)boraadamantyl 113

Mes2BPPh2

Co( CO ) ( PMe3 ) ( n4-C5H7BPh)

130 114

115

[NMe3ph1 [CpFe(p-n5-C4H4BPh)Cr(C0131 220 116

Fe ( CMeOBF2C€CMe-CH2 ) ( CO) ( Cp) 117,118

Fe ( CO) ( Q5-C4H4BPh) 213 119

- 120

121

118

118

BFe3CgH5Og 126


No.

159

160

161

162

163

164

165

166

167

168

169

170

171

172

17 3

174

175

176

177

178

179

180

181

182

183

184

185

186

187

188

189

190

Details

151

130

130

104

173

213

153

190

433

Re/.

127

112

112

128

129

129

129

129

130

131

132

122

133

134

135

136

137

138

139

122

140

141

136

142

143

136

136

143

136

144

125

125

434

No.

191

192

193

194

195

196

197

198

199

200

201

202

203

204

205

206

207

208

209

210

211

212

213

214

215

216

217

218

219

220

221

222


Derails

208

208

E

243

185

185

Rd.

145

128

115

96

96

146

147

148

136

149

150

151

151

152

153

153

153

154

155

156

157

158

159

160

16 1

161

162

163

164

164

165

166

Structures determined by Diyraction Methods 435

No.

223

224

225

226

227

228

229

230

231

232

233

234

235

236

237

238

239

240

241

242

243

244

245

246

247

248

249

250

251

252

253

Formula

B10C8H16

B1 lFeC4 5H40N4

B16Pt2C31H55P3

B17m2C20H49 B18C4H20S4 1 2-

[ B18CNqH16Br6 1-

[B18COC4H2012 I- [ B18CoCqH211 1-

B1 8CoC7H2 5'2'

B18SiC4H22 BiC9H12C13

BiC30H2506S2 BiFe3CgH3O9

BiFe3C11H3010

I BiFe4Cl6OI6 I 3-

Bi2CgH12C16

[ Bi2CoFe2C10010 1-

[Bi2Fe4Cl3Ol3I2-

[ Bi4Fe4C13013 I 2- Bi3W3C14H3013

CaC20H30 CdSi4C24H44N2

CeLiC28H50C1202

C&gH18C102P2

t CoCl0HlO I +

~ c ~ l O H 1 O l +

CoC10H17N205

COC11H18N03

2% 7'l2'

'OCl 3H261P

CoC15H20Cm604 [ COC15H31N405P 1'

Derails Ref.

167

168

169

170

160

171

172

173

174

175

176

177

178

178

179

176

180

180

181

182

E 183

184

185

186

187

223 188

189

190

191

192

193

194


No. Fomla

254 CoC16H1203P

255 CoC16H23N604

256 [ CoC16H38P3]'

257 CK17H17C1N304

2 58 [ CKl7H2 5N2P I' 259 [ CoC18H24N5 ] 2+

260 C O C ~ ~ H ~ ~ N O P

261 COC18H2803P

262 [ COC18H29N502 I' 263 [ CoC18H33PS 1'

264 I +

265 [ CoC20H31N504 1'

266 CoC20H33P2

267 COC21H15N202

268 CoC25H2202

269 COC28H44

270 CoC2gH20C1204P

271 [ CoC30H37N402P 1'

272 [ COC32H290P2] 2+

273 CoC33H25N2

274 [ COC33H3503P3 I' 275 CoC34H28P2

276 [ CoC34H3803P3 ] 2+

277 C O C ~ ~ H ~ ~ N O ~ P

278 CoC37H2502

279 [ CoC38H34N202P2]+

280 [ C O C ~ ~ H ~ ~ N O P ~ I+ 281 [ CoC38H36P2S 1'

282 C O C ~ ~ H ~ ~ N O ~ P

283 CoC42H3502

284 [ CoC42H38N02P]'

285 C&46H42N3

Details

173

Rej.

195

193

192

196

197

198

199

195

co ( co 1 ( Pph3 1 ( n3-CH2CHCHCH=CH2 1

Co( 1-norbornyl )

204

205

CO( C(0)CH2C6H3C12-2, 6) (CO) 3( PPh3) 206

194

207

208

Structures determined by Diflrac :tion Methods 437

No. Formula

286 [ CoCq7HqgN02P3 I +

287 [ CoC51H440P4]+

288 CoCrC15H907

289 CoFeC15H707

290 COFeIrRuC16HgO10P

291 CoFeNiC17H1506

292 CoFeNiC42H3005P

293 CoFeRh2RuClgH1408P

294 CoFe2C14H908

295 [ CoGeC1,HqlP3 I +

296 COMgC16H26Br02

297 COMgClgH30BrN2

298 CoM”C1,Hl3O5P

299 CoM”C24H1606

300 Co~c26H3702PS

301 CoMoC12H15Br2N

302 COMOcl4H5F605

303 CoMo2ClgHl3O7

304 CoMo2C44H28010P2

305 CON~OSC,~H~~O~

306 C O N ~ R ~ C ~ ~ H ~ ~ O ~

307 CoNi2C16H1305

308

309 C O R ~ C ~ ~ F ~ ~ O ~

310 CoRuC25H37013P4

311 CoRuC36H2506P2

312

31 3 CoRuWClgHl 508

314 CoRu3C36H27010P2

315 [ CoSiC17HqlP3 1’

316 CoSi2C16H250

317 C O W C ~ ~ H ~ ~ O ~

SlniChlre Details Rtf.

213

214

206

21 5

216

217

217

216

77

218

219

219

37

220

201

221

222

223

210

217

211

223

224

225

226

227

228

229

230

218

133 231

232


COW( CO) ( Cp) ( n4 : nl-( pTo1) CCEtCEtCOH) 233

co2(co) 4 ( p - n 6 - ~ 5 ~ ~ ~ ~ ( ~ ~ 5 ) ~ ~ ~ ~ ~ 5 ) 234

237

238

239

240

241

242

243

244

Co2Ni ( CO 1 ( Cp 1 ( p3-CC02Me 223

225

247

245

245

248

233

233

249

250

251

252

253

254

255

P LZ

E LZ

ZLZ

T LZ

0 LZ

692

LBT

89Z

P9Z

L9Z

99z

s9z

P9Z

E9Z

E9Z

€92

z9z

z9z

T9Z

09z

6SZ

8SiZ

OEZ

EZZ

LE

LE

LS z 8L

9sz

ESZ

ssz ESZ

YaI

EEZ

DOT

6EP


No. Formula

382 CrC14HZ4P

383 [CrC14H3202P4 1' 384 [CrC14H3302P4 1'

385 CrC15H11N06

386 CrC15H1509

387 CrC15H17N06

388 CrC16H1005

389 CrC16H1203

390 CrC17H1803

391 CrC18H1408

392 [ CrCl9H8NO6]+

393 CrC21H18N05P

394 CrC25H2002P

395 CrC26H40N2

396 [ CrFeCgOg 1 2- 397 [ CrFeC9H09 I- 398 CrFeCI5Hl0O5

399 CrFeC17HZON06P

400 CrFeReC20H7012

401 CrFeSe2C14H1004

402 CrFe2C13HO13

403 CrFe2C20H19C1012P2

404 CrFe2C29H33011P3

405 CrFe4C18018P2

406 CrGeC11H11C12N06

407 [ CrSe2C7H502 1- 408 CrSiC17H1404

409 Cr2C10H10S4

410 Cr2C12H16C12

411 Cr2ClSH807S

412 Cr2CI9Hl4O6

413 Cr2C20H19010P

Dernils RcJ.

270

275

275

276

238 277

270 I 279

79

280

281

277

223 282

283

284

285

286

286

281

288

200 289

287

223 43

248 290

223 290

225 291

292

187

293

294

295

296

297

298

Structures determined by Difraction Methods

No.

414

415

416

417

418

419

420

421

422

423

424

425

426

427

428

429

430

431

432

433

434

4 35

4 36

4 37

438

439

440

441

442

443

444

445

F o m &

5l2

Derails

243

218

233

223

223

153

233

441

Ref.

299

300

301

298

290

291

302

293

295

188

187

303

304

305

306

307

4

308

309

310

83

86

311

10

311

312

313

314

314

315

316

317


No. Fonnula

446 Cu2C44H38N402

447 Cu2m6C32H16018 448 Cu3Fe3C12012 1 3-

Derails Rqf.

306

318

319

319

320

321

322

323

324

325

325

326

327,320

329

330

143 331

332

333

330

334

272

335

336

337

338

339

340

341

342

343

344

163 345

443 Structures determined by Dlrraction Methods

No. Fomla

478 FeC17H37102P2

479 FeC18H1802

480 [ FeC18H3202Pl'

481 FeC20H1402

482 FeCZoHZoN

483 FeC20H22

484 FeC20H29BrN03P

485 [ FeC20H30 1'

486 FeC20H45011

487 [ FeC21H1603P 1-

488 FeCZ1H19N03

489 FeC22H17PS4

490 FeC23H28P

491 [ FeC25H61013Pq 1' 492 FeC27H2704P

493 FeC28H2705P

494 FeC29H2203P2

495 FeC30H40

496 FeC33H2903P

497 FeC35H3105P

498 FeC35H3105PS

499 FeC36H36C12N4

500 FeC37H4303P

501 FeC38H35P

502 FeC39H3002P2S

503 FeC39H34N02P

504 [FeC45H45C1N51+

505 FeC58Hq2

506 FeC71H72N1005

507 FeGeC3qHq606

508 FeGeSiC2,H2502

509 FeflgC13fl16ClN

350

351

352

173 353

355

3 56

3 57

358

359

360

[45](1,2,3,4,5)Ferrocenophane 36 3

Fe(~-C(0)CMe=CmeSPh)(cO)(P(OPh)3~(Q) 365

368

369

364

Fe( CO) (N2C3H3Me) (4-N bonded macrocycle) 173 371

eq-Fe(CO) - 4Ce(OC6H2MeBut2-41216)2

Ph3GeSiMe2 ( Fp)

338

372

444

No. Formula

510 FeHgC25H28C1206P2S2

511 FeIrC35H32C103P2

512 FeMnC41H350P2

513 FeMoC12H1512N

514 FeMoC18H1205S

515 FeMoClgH17N04

516 FeMoCZOH1605

517 FeMOC21H1606

518 FeMoC27H2304P

519 FeMo2C27H3008

520 FeMo2Te2C1 5H1 203

521 FePdC26H28C12NP

52 2

523 FePtC2gH22Br204P2

FeP tC2 8H22 I 203P2

524 FePtC34H28C12P2

525 [ FeRhC18H1603 I +

526 FeRhC18H1903

527 FeRhC26H3204P

528 FeRhC30H22C105P2

529 FeRhC36H3103P2

530 FeRu2C12H10NO12P

532 [ FeSe2WC808 1 2+

533 FeSiC15H2303P

534 FeSiC39H3103P

535 FeSi2C19H3302P

531 [ Feb3C16H1om16P2 1-

536 FeSi2C23H28F6N02P

537 FeSi3C23H43N

538 FeSnC34Hq606

539 FeV2Cl2HI4N2O2S4

540 FeV2C15H1403S3

541 FeV2C15H1403S4


strumm Details - Fe(CScRcRs)(CO)2(PMe2Ph)2Hgc12 (R-C02Me)

Fe P-C( SiMe3 1 1 ( CO) ( cp* 1 r Fe{C(0)CCF3CCF3iPhN(SiMe3)2}(CO)(Cp)

111

223

R4-

374

375

376

221

377

378

377

377

379

380

381

382

383

384

385

386

387

388

384

387

389

389

390

391

392

393

394

395

3 38

396

396

396

445 Structures determined by Diffraction Meihods

Structure Derails ReJ. No. Formula

286

286

397

288

398

549 FeW2ClgH1207

550 FeW2C27H2007

551 FeZrC36H32C102P

552 Fe2C8H406S2

553 Fe2C10H607S2

554 Fe2C12H6O6S2

555 [ Fe2C14H10C104 I +

556 Fe2C14H13N07

557 Fe2C14H1806P2

558 Fe2CI5Hl4O2

559 Fe2C15H1,0ePS2

560 Fe2Cl,jHl8o7P2

561 Fe2C16H20N2o6

562 Fe2C16Hz206P2

563 Fe2Cl7H16O3

564 [ Fe2C17H341N2013P4 I + 565 Fe2C18H10O9

566 Fe2C18H1206

567 Fe2C18H20N2O8

568 Fe2C18H24N206S2

569 Fe2C20H1008P2

400

401

403

404

405

Fe2 ( CO ( p-n2-MeCCNEt2 406

407

408

407

411

[ Fe21 ( CO 1 ( P- I P ( OMe 1 1 2NEt ) I [ PF6 I Fe2 ( CO ) ( p-Q4-cHCHC ( OMe ) CoCoph)

412

280 413

414

410

415

416


No. Fonnula

574 Fe2CZOH17F3N3P3

575 [Fe2C20H181+

576 Fe2C20H2206

577 Fe2C21H26N207

578 [Fe2C22HlgNO12+

579 Fe2C22H2004P2

580 Fe2C24H2308P3

581 Fe2C24H2508 I +

582 Fe2C24H28N208

583 Fe2C24H34N202S2

584 Fe2C24H42N306

585 Fe2C25H18N208

586 Fe2C25H42N307

587 Fe~C26H1806P2

588 Fe2C26H2006P2

589 Fe2C29H2606P2

590 Fe2C32H21N06P2

591 Fe2C32H340

592 Fe2C34H2408P2

593 Fe2C34H28N02

594 Fe2C34H3404P4

595 Fe2C34H3705PS2

596 Fe2C34H4206P2

597 Fe2C36H4608P2

598 Fe2C44H30N06P3

599 Fe2C46H46N4

600 Fe2M02Te2C17H1007

601 Fe2Mo2Te3Cl6Hl0O6

602 Fe2Nicl4H8o8

603 Fe2RhC14Hg08

604 Fe2Ru2Cl3H2OI3

605 Fe2SiC40H3603P2

410

423

424

425

424

426

163 427

163 427

428

351

248 429

430

426

431

432

140 433

428

434

435

436

77

4 37

4 38

Structures determined by Difraction Methods 447

NO.

606

607

608

609

610

611

612

613

614

615

616

617

618

619

620

621

622

623

624

625

626

627

628

629

630

631

632

633

634

635

636

637

Formula

Fe2Si2C16H16F205

Fe2Si2C22H58P6 t Fe2WC20H12N08 I-

Fe2wc27H2906P

Fe2WC27H3 4'6'2

Fe 2WC 3 lH2 3'6' t Fe 3 ~ 8 ~ ~ 2 0 9 I - [ Fe 3cg0gs 1 2-

Fe3C10H7N08S2

Fe3C16H8010P

Fe3C17H9011P

Fe3C19H15"10

Fe3C19H17"10

Fe3C22H26N208

Fe3C23H15010P

Fe3C23H30N3011P3

Fe3C24H30N3012P3

Fe3C26H1908P

Fe3C27H1909P

Fe3C27H3701 5'5

Fe3C32H2109P

Fe 3C36H2801 3'2

Fe3C36H3006S6

Fe3C37H24011P2

" 3C37H4 4'9'2

Fe3mC40H68017P5

Fe3m2c2 3H1 0'1 3'2

Fe3Rhc30H2508P2

Fe 3*'3 lH2 5'9'2 Fe3Rh2Cl7H5Ol3 1-

[ F ~ ~ R ~ ~ c ~ ~ o ~ ~ I 3-

Fe3Te2c1 lHgN07

448

No.

6 38

6 39

640

641

642

643

644

645

646

647

648

649

650

651

652

653

654

655

6 56

657

658

659

660

661

662

663

664

665

666

667

668

669

Formula

Fe3WC15BrO15P

[ Fe4Cl4Ol4P 1 -

[ Fe4C20H20S5 12+ Fe4C16H12012P4

Fe4C24H18012S3

Fe4C27H23013P3

Fe4c2 SH2301 4'3 Fe4C31H2306 I+

Fe4mC20H5015P2 [ FeqPK16016 1 2-

1 FeqRu2C22022 1 2-

Fe4WC40H3602 [ ~ e ~ ~ ~ ~ m ~ ~ 1-

Fe 5mc2 3H501 8'2 1 Fe6C12012S6 1 2-

Fe6C14N2015 12- Fe6M02C6C1606S6 ] 4-

Fe6W2C48H42012S6 3-

Fe10T16C36036 1 6-

GaC27H33

GaC32H42P2 GaLiSi8C26H70C1202

GaMo*C49H4 2N603p2 GaNoSnC31H27N603

GaRe3C62H4 5'2'8'3

GaRhC11H12C1N302

GaRhC12H1 SN302

-2'qH14

-2'1 2H2 2N4S2

Ga2C16H16Br4

Ga2C18H20Br4

Ga2C20H48P2


Details

248

189

E

233

Ref.

291

4 58

422

459

460

461

461

462

291

463

464

465

444

291

466

444

467

468

469

470

471

472

308

473

474

475

475

476

477

478

479

47

Structures determined by Difraction Methods

No. Formula

670 Ga2C32H72P2 671 Ga2Re4C18018

672 Ga4C24H24X8 673 GdCIOHIOBr

674 [ GeC3F11]-

675 GeC8H18N2S4

676 GeC10H15C130

677 [GeC13H3C1804

678 [GeC13H1104 I-

679 [@C15H15Sq I- 680 [GeC18H5C1804

681 GeC18H1304 1- 682 GeC24H10F8

683 GeC80H70

684 GeSe2C16H18

685 [ GeSiC20H31 1’

686 GeSiC21H24

687 GeSi2C17H34

688 GeSi2WC22H3405

689 GeSi4C14H38

690 GeSi6C28H58

691 Ge2IrSi8C26H72C1N402

692 Ge2PtSe2C10H28C12

693 Ge2Si8C28H76

694 Ge3C32H3802 695 Ge3C36H30C12

696 &3‘3eH36

697 &3‘4eH40

698 Ge3C54H45P7

Derails

233

168

E

I:H{Ge(TMSA)2){CH2SiMe2N(SiMe3)deCl(-)(CO)2

ts-PtC12(SeMeCH2GeMe3)2

[@{a( siMe3 1 21 1

Ph4e2 ( fi-02GeBut2 1

(GePh2C1I2GePh2

Ph3GeGeMe2GePh3

Ge3Ph8 P7( GePh3) 3 . 2THF

449

Re$

47

480

481

482

483

484

485

486

486

486

487

487

488

489

490

491

372

492

493

494

495

496

497

498

499

500

501

502

503

496

504


No. Formula

701 Ge4C48H40C12

702 Ge4C60H50

703 Ge5C72H60

704 Ge6C24H54 705 HfC26H4402

706 HfSi2C20H48N4

707 Hf2C29H3203

708 Hq3H60S2

709 HgC4H6N6

710 [ HgC4H7N6 1' 711 HgC4H9W2

712 HgC5H10N203

713 HgC6H7NS

714 HgC6H8N2S

715 HgCgHgC102

716 HgCllHIOBrN

717 HgC12HllN50

718 HgCl8Hl7C1O3

719 HgC18H2206

720 HgC23H35F302

721 [H$32H30N3 1'

722 [ H@s20c50048 1 2- 723 HgPtWC50H35C1503P2

724

725 HgSeC4H8C12

726 HgSi4C24H44N2

727 Hg!l?e2C24H32C12N2

728 [ H ~ ~ C S H ~ N ~ 1' 729 [Hg2C6H4C13]-

730 Hg2C6H7N50

731 [Hg2C6H13N2O3 1'

7 32 Hg2C1p12C1202s4

Stnrcntre

MeHg(8-azaadeninato).4H20

MeHgNH2CHMeC02

MeHg(glycylg1ycinato)

HgMe(SC5H4N-2)

MeHgS(C4N2H2Me-2)

HgC1(C6H4CO2Et-C)

8-(BrHgCHMe)(CgH6N)

Details Ref.

500

502

505

506

98 507

508

509

510

511

511

512

513

190 514

51 5

516

153 517

518

153 519

520

521

522

a5

523

524

525

184

526

511

527

518

513

528

Structures determined by Di$raction Methocis 45 1

No. Formula

733 [ Hg2Cl2Hl101+

734 H92Ru7C34H18022 735 [ H ~ ~ C Z H ~ W ~ 1'

736 [ Hg-jC6H11N6 1' 737 [ Hg3C7H13N5 I 2+ 738 Hg3C8H11N5

739 Hg3C36H24

740 [ Hg4CgHI4N5 I +

741 [Hg5C14H23Nlol+

742 Hg6C4H3N7025

743 InC10H15

744 InLiSi8C26H70C1202

745 In2CH2C13X

746 [ In2C30H36N1106 1' 747 In2LiSi6C28H7502

748 In2Nb3C36H45C12

749 In4Si12C40H11407

750 IrCllH31C102P3

751 [IrCl3Hl7ClO21+

752 [ IrC16H33C1P2]+

753 IrCl9Hl5C1N40PS4

754 IrC1gH36P

755 [IrC24H14F412N21+

756 IrC24H48C1P2 --.

757 IrC25H37N6

758 IrC30H24C1NP

759 IrC33H40 Ir(PMe2Ph)3(n3-ind)

760 IrC37H35

761 IrC40H3304P2 Ir ( C02Me 1 ( CO) ( PPh3

762 IrC40H34C102P2 I r (CH2C(0)cl12)C1 (CO) ( PPh3 1

763 IrC41H30F4N03P2 Ir { NC ( O)CF2CF2CO} ( CO) ( PPh3

764 [ IrC42H58N206 I+ ( + ) -[ :r ( n2-CHPh-C( d O M e ) C02 (menthyl) 1 I [ BF4 1

I r ( PPh3 ) ( 112-NCC6H,C1-p) ( Cp 1

Ir ( cod) ( h5-C9H3BzPh2Me-1 I 2 , 3 I 7 1 - -

Ref.

529

530

531

511

532

533

534

533

532

531

535

472

536

537

538

539

540

541

542

54 3

544

545

546

547

548

549

550

551

552

553

554

555

452

No. Formula

765 IrC43H30F502P2

766 [ IrC44H36F6P2]+

767 IrC44H4105P2

768 IrC44H57N4

769 IrC45H38F6P2 I+ 770 [ IrC50H54NP3]+

771 IrC51H40C102P2

772 I rC53H51P4

773 IrCs3HqgC1O2P3

774 [ IrMoC36H38P2]+

775 I rRhC30H57C108P2

776 IrSiC32H40P

777 IrSiC32H40P

778 IrSi2ClgHq71NP2

779 IrSi2C22H47

780 IrSi2C35H47C1NP2

781 1 mc36H3304P2

782 [ 1 I%C36H3#2]+


~rC1(C6H4C(0)&=CPhOPPh2) ( PPh3)2.Sv 561

564

565

566

567

(CO) 4WI rH( cod 1 (p-PPh2 ) 2. sv 375

784 Ir2Cl6HZ4Cl2

785 Ir2C16H26C1203

786 Ir2C23H35N21+

787 Ir2C29H40

788 Ir2C38Hq7N3

789 [ Ir2C53H4503Pq 1'

790 Ir2C59H53C12N05P4

791 [ Ir3C606S2 1-

792 Ir3MoC16H5011

793 [ Ir3Se2C6O6 1-

794 I r4C16H16010P2 795 Ir4C54H8806P4

796 I r6C17H3017 1-

57 1

571

572

228 573

574

57 5

576

577

578

577

579

62

580


No. Fonnula

797 K2Yb2C36H6006 798 LX15H15

799 LdC75H63P6

800 LiC14H25N2

801 LiClgH230

802 LiLuC40H46N2P2

803 LiNi2C17H40N3

804 LiSiC32H59C1N02

805 Lisic36H67m3

806 LiSi4TiC24H47C1N30

807 [ LiSi6C20H54 I- 808 LiVC17HZgN2

809 Li2C32H48N6

810 Li2C32H52N202

811 Li2C34H66N404

812 Li2Si2C25H55N5

813 Li2Si6C20H5406

814 Li2Si6C20H56N602

815 Li2Si8C32H8204

816 Li4CZOHq8N4

817 Li4C44H,2N804S4

Li4C84H112014P4 819 Li4Si2C20H48N4

820 Li6Si2C36H64N6

821 Li6Si6C24H66

822 LuC14H18C10

823 LuC15H15

824 [ LuC16H36 1-

825 Lu2C28H3802

826 [ Lu2C30H31 I- 827 MsClOH2202

828 MgSi2C13H36N2

Denails

154

123

100

133

233

233

173

453

Re/.

581

582

58 3

584

585

586

587

588

588

589

590

591

592

593

594

595

596

597

598

599

600

601

602

602

603

604

605

606

607

607

608

609

454

No. Fomla

829 MgSi4C24H44N2

830 M9W2C72H8006

831 Mg2C14H34N2

832 Mg2C24H50N2

833 Mg2Si4C20H54N2

834 M94C28H4004

835 MnC13H8BrC1305P

836 MnC14H15C102

837 MnC15H1903

838 MnC17H12Br02

839 MnCl8HllN2O4

840 MnC18H2303

841 MnC18H38P3

842 [mCzoH17N303 1’ 843 MnC23H40P3

844 MnC29H22N03S

845 MnC35H3303P2

846 M ~ M o C ~ , H ~ ~ O ~ P

847 MnMoC29H2606P

848 MnPtC17H3105P2

849 MnFteCloOlo

850 MnReSi2C17H23N206P

851 MnSiC20H18F02

852 MnSiC22H280P

853 MnSiC24H2702

854 MnSi2C16H26

855 Mn2C10F408

856 Mn2C11H408

857 M”2C14H808

858 Mn2C14H1005S

859 Mn2C16H1606 860 Mn2C17H1604S


Derails

115

27 3

N at 120

238

193

Rel.

184

610

611

611

612

613

614

615

616

617

618

619

620

621

620

622

623

624

624

625

626

627

628

628

628

629

630

631

631

632

619

633

Structures determined by Diffraction Methods 455

No.

861

862

86 3

864

865

866

867

868

869

870

871

872

873

874

875

876

877

878

879

880

881

882

88 3

884

885

886

887

888

889

890

891

892

Fonnulo

m2C20H29N208P

m2C21H1705P

Mn2C23H21N304

m2C24H2804S

m2C24H3404P2

m2C24H4106P3

Mn2C26H46C12N4S2

[m2C31H16N506 I +

m2C31H4507P2 1'

m2C40H3004P2

m2SnC24H1 SNZo8 [ ~ 2 % ~ 2 0 ~ l 5 0 4 I- [ ~ 2 % ~ 2 o ~ l 5 0 4 I+ [MoC41304 I-

[moc615061-

MoCgHgBr30

M°C9H11C12

Moc9H1 4'3'3

Mocl OH1004S

M°C11H12N205

M°CllHl SNO

M°C11H1802

M°C11H2704P3S

M°CllH281 2OP4 [MoC12H12103 I +

M°C12H1202

Mocl 2H1203

M°C12H13N

M°C12H141N02

Mocl 2H1403

M°C12H2703P3S2

Details Rqf.

249

228 634

635

636

213 634

637

638

639

637

640

233 641

642

243 643

238 643

644

644

645

185 646

647

648

649

650

100 651

6 52

653

644

654

114 655

656

657

6 58

659


Mo( CO) (bipy ) ( NC5H4NHC5H4N)

Details R&

660

272

661

662

663

664

644

665

6 59

663

666

661

660

669

670

671

672

663

613

674

615

676

677

612

659

678

679

680

681

602

683

604


No.

925

926

927

928

929

930

931

932

933

934

935

936

937

938

9 39

940

941

942

943

944

945

946

947

948

949

950

9 51

9 52

953

954

955

956

457

Derails Ref.

114 685

686

185 687

688

675

689

690

691

692

693,694

140

118

148

223

223

692

695

696

697

698

699

700

399

701

702

703

704

705

706

625

707

707

675

679

673

673

708


No. Fonnula

957 MOSi2C16H3104P

958 M O S ~ ~ C ~ ~ H ~ ~ F ~ O ~ P S

959 MoSnC12H17C1

960 MoSnC13HZ0

961 MoZrC38H3004P2

962 MoZr2C38H30C1204P2

963 [ Mo2Cl5HlgO2S3 I + 964 Mo2C16H806

965 [MO2C1&4012S2 12-

966 Mo2C17H1803

967 M'2C18H20N2010S2 968 Mo2C18H2002S2

69 M02c1 oH3 0 F6°2 0 4 970 MO2C18H3408

971 M02C19H1406

972 M'2C19H1604 973 MO2C1gH1804

974 [Mo2C19H19Sdl+

975 IM02C19H19S41+

976 M O ~ C ~ O H ~ ~ O ~ S ~

977 Mo2C20H24N404S2

978 Mo2C21H20N208

979 Mo2C22H1706PS2

m2C22H2204 981 [ Mo2C22H2804S2 1 2+

982 MO2C22H36Sq

983 M o ~ C ~ ~ H ~ ~ ~ ~

984 M'2C24H28 985 M02C24H2803

986 M02C25H20N202

987 Mo2C25H20011 988 Mo2C26HZ004P2

Stmmre Derails Ref.

708

708

709

709

710

711

712

713

714

715

716

717

718

116 719

713

720

715

721

722

723

477

724

725

7 26

727

728

726

729

726


No. Formula

989 Mo2C27H20N204

990 Mo2C27H2605

991 M02C28H30F6N204

992 M02C28H36N206

993 Mo2C30H32

994 Mo2C32H3202

995 Mo2C33H2703P

996 Mo2C34H20N2010P2S

997 Mo2C40H32N1006 998 Mo2C42H42

999 M02C43H88N206

1000 Mo2C43H88N206

1001 Mo20S3C23H13012

1002 Mo3C23H15C1F120

1003 Mo3C24H2004

1004 Mo4C32H44S4

1005 Mo6c28~64clloP2

1006 NaC26H53N4

1007 NaPrC28H50C1204

1008 Na4CS2Hg2N8

1009 NbCllHIOCIO

1010 NbC18H23

1011 NbSi6C17H51N4

1012 Nb2C24Hz8C120

1013 Nb2SnC22H27C1

1014 Nb2SnC26H28C1202

1015 [NiCl1Hl5N2O21+

1016 NiC17H3002P2

101 7 Ni C1 9Hz 4N5S2

1018 NiC21H27F8N2P

1019 NiC35H3304P

1020 NiC35H3903P

Details

119

114

138

117

459

ReJ.

724

732

733

724

734

734

735

736

737

7 38

739

739

703

646

715

740

741

742

743

744

539

745

508

539

746

7 46

747

748

749

750

751

7 52

460

No.

1021

1022

1023

1024

1025

1026

1027

1028

1029

1030

1031

1032

1033

1034

1035

1036

1037

1038

1039

1040

1041

1042

1043

1044

1045

1046

1047

1048

1049

1050

1051

1052

Sfructure


Details ReJ.

753

754

754

213

755

756

757

758

7 59

760

396

100 587

761

762

763

764

765

765

755

766

766

767

768

223

769

770

771

772

773

773

774

775


No. Formula

1053 [ OsC3H21N50 1 2+

1054 OSCIOHIO

1055 OSC12H20C120S

1056 [OsCl3Hl5O31+

1057 [ O S C ~ ~ H ~ ~ I O ~ P ~ ] +

1058 OsC20H30

1059 OsC27H4gC10P2

1060 [OsC35H400P]+

1061 OSC37H30F3NOX2

1062 OSC39H27N205P

1062a OsC39H33Br03P2

1063 OSC43H30C16N304P

1064 06C44H36C102P3

1065 OSC45H37C10P2

1066 06C45H3903P3

1067 OSPt2C59H4505P3

1068 OsRh2C41H5902

1069 [OsSi4Cl6Hq4N1-

1070 OsSi4C17H47N

1071 Os2C14H6012

1072 Os2C18H10106P

1073 [Os2C21H3103 I +

1074 Os2C26H54

1075 Os2C27H34

1076 Os2C30H24022

1077 Os3CgH2013S

1078 Os3CllH2010

1079 Os3C11H7N09S2

1080 Os3C11H11NOgS

1081 Os3C12H2011

1082 OS3Cl3H5ClO8

1083 Os3C13H51011

Structure Details Rqf.

776

777

778

779

780

OS(ep*), 781

783

784

785

5

Os{PH(OMe)Ph)(CO)2(PPh3)2 785

“Bu4 1 [Om( m2SiMe3 1 1 113 788

Os(NMe 1 ( CH2SiMe3) 114 788

794

795

446

796

795

797


No. Formula

1084 Os3C13H5NO10S2

1085 Os3C13H80g

1086 [Os3C14H4NO13 I- 1087 [Os3C14H5013 I -

1088 Os3C14H6012

1089 0s3Cl4H8Og

1090 Os3C15H5C1010

1091 OS3Cl6HgNOll

1092 Os3C16H18Br2016P2

1093 Os3C17H13N08S

1094 Os3C18H8010

1095 Os3C18H8010S

1096 Os3C18H14NOgS

1097 Os3C22H23N20gP

1098 Os3C30H19010P

1099 Os3C33H2408P2

1100 Os3C36H22010P2

1101 Os3C59H440gP4

1102 Os3PtC25H2209P2S2

1103 Os3PtC48H32011P2

1104 Os3ReC38H22014P

1105 Os3SiC22H14010

1106 Os3SnC12H2C12011

1107 Os3Sn2C16H20010

1108 Os3WC25H14012

1109 Os4C12H2012S

1110 [ Os4C12H4012]-

1111 Os4C14H7NO12S

1112 Os4C15H4013S

1113 Os4C15H6013S

1114 Os4C16H6014S

1115 Os4C17HgO14P

Rel.

799

800

801

798

802

803

797

804

805

806

807

808

806

809

810

811

362

812

813

814

815

816

817

816

818

819

820

819

821

821

821

822


No.

1116

1117

1118

1119

1120

1121

1122

1123

1124

1125

1126

1127

1128

1129

1130

1131

1132

1133

1134

1135

1136

1137

1138

1139

1140

1141

1142

1143

1144

1145

1146

1147

Formula

0s4C21H12013S

0s4C31H16013S

0s4PtC28H22011P2S2 Os4PtC31H15013PS

0s5C23H6015

0s5C42H2 4'1 5'2

OsSPtC3 3H1501 5"

0s5PtC51H30015P2S

0s5WC37H1 5'19'' [ os6c18018p 1-

0s6C18H2019S2

"6'1 gH2'19

"6'1 gHgNOl 6'2

0s6C22H6N020P

0s6C22H7021P

0s6C28H6020

0s6C34H30016P2

0s6C35H1 5'17'

0s6Pt2C30H30022P2

0s6Pt2C32H24016

0s7C21H2021

0s7C22H2022

PbC8H1203

PbC21H1804

PbC50H42P4

PbC80H70 PdC6Hl5fO2S2

pdcl lH1 7'1°2

PdC13H171N2

PdC14Hl 4 PdC15H23C1NP

Pb( CH( PPh2 ) 2] ( Ph2P&Ph2 ) . Sv 130 837

Pb( h-C5Bz5 168 489

PdI(CH2S(0)MeCH2)(CH2SMe20) 838

Pd( acac ) ( )73-CH~eCCH2~2C1 ) 839

fac-WIMe3 (bipy) 840

Pd ( '13-C3H4Ph 1 ( Cp 1 185 687

PdCl( n3-CH2CMeCH2 1 { PhP( OCH2CH2 1 2 ~ e ] 841

1 Pd( TMED) ( n3-C3H4Ph 1 [ BF4 1 185 687

-

464

No.

1148

1149

1150

1151

1152

1153

1154

1155

1156

1157

1158

1159

1160

1161

1162

1163

1164

1165

1166

1167

1168

1169

1170

1171

1172

1173

1174

1175

1176

1177

1178

1179


Snucture Details Rqf.

842

843

844

Pd( hfacac 1 ( n3 : n3 4 CH2CHCHCH2 1 2]

12

2. sv

853

854

851

855

856

857

8 58

497

859

860

861

839

862

863

554

123 864

865

866

867

868


No.

1180

1181

1182

1183

1184

1185

1186

1187

1188

1189

1190

1191

1192

1193

1194

1195

1196

1197

1198

1199

1200

1201

1202

1203

1204

1205

1206

1207

1208

1209

1210

1211

Slrucrure Details Ref. . - {Pd(PMe3) (,v-01:nL-SeZCPMe3) l2 { PdCl ( ri2-&QINButSiMe2i!13ut (p-Cl) 1

869

870

874

875

876

h2 ( I~"-CH~=CHCH~CM~,CH,SN~&~ 876 PtC12(CH2C1)(~2-CH2CHCMe2CH2NMe2) I 1 (2 isomers) 876

PtClMe2(CH2Cpz2CH2C1) 878

878

879

880

881

882


No. Fomla

1212 PtC38H30N202P2

1213 PtC39H30F6P2S

1214 PtC39H32F604P2S2

1215 PtC39H38103P3

1216 PtC40H20F10

1217 [ PtC47H44C1NF'3 1'

1218 PtC50H38N202P2

1219 [PtC50H430P2]+

1220 PtC52H4203P2S

1221 PtC52H4204P2S

1222 [ PtC55H47P3X]+

1223 PtC57H47P3

1224 PtC5gHq8P2

1225 PtReWC23H2509P2

1226 [ PtRh8ClgOlg ] 2-

1227 PtRuC16H20C12S4

1228 [ PtSbC49H53N02P2]+

1229 PtSe2C8H10C14

1230 Pt"hC47H49P3

1231 [PtWC21H3902P2

1232 [PtWC27H4302P2

1233 PtWC37H4505P3

1234 Pt2C12H32S2

1235 Pt2C12H3412P4

f

f

1236 [ Pt2Cl 5H27N1 o06 ] 3+

1237 Pt2C18H18N204

1238 Pt2C19H23C12N302

1239 Pt2C21H29N302

1240 Pt2C24H28F2N402

1241 Pt2C24H30N402

1242 [ Pt2C56H541P4S4 ]+

124 3 Pt2C58Hq21 4N2P2

2 2 isomers)

Derails

185

. sv

C&-Pt{C6H4C( O)NC6H4bPh2) (P- h2C6H4NHCOP.*)

trans4 Pt ( CPh-CHPh) ( H20) ( PPh3 l2 I [ HC( S02CF3 1 1

Pt(CH(COPh)S(0)CPh)(PPh3)2.Sv

it { M ( COPh ) S ( 0 1 2&HCOPh 1 ( PPh3 ) 2. Sv

- CC&-[P~X(CH~PP~~)(PP~~)~]I.SV (X=Cl,I)

Pt ( PPh3 ) ( n2-C12HeC=PXy) . SV

Ref.

892

893

894

895

896

897

898

894

899

899

900

901

902

903

904

905

906

907

908

909

910

911

912

913

914

912

912

912

912

912

915

916

Structures determined by Drfraction Methods 467

No. Formula

1244 Pt2C65H53C12N02P4

1245 [Pt2C72H61P4]+

1246 Pt2C76H116N4S

1247 Pt2W3C45H3606

1248 Pt3C57H4503

1249 [ Pt3C76H660P6 2+

1250 [ Pt3C77H66NOP S]+

1251 [ Pt3C86H80NqPq 1 2+

1252 [ Pt3CgoH84N6P2 1 2+

1253 Pt3W2C46H4804

1254 Pt3W4C60H4808

1255 Pt4C29H6005P4

1256 Pt4W4C60H4808

1257 Pt5C75H600gP4S3

1258 [ReCIOHlO]+

1259 ReC10H15C104P

1260 ReC10H15C120

1261 ReC12H15Br202

1262 ReCl2HI5I2O2

1263 ReC14H30C1202P2

1264 ReC15H30C103P2

1265 ReC17H20N03

1266 ReC18H2503

1267 ReC18H2702

1268 [ ReC23H1505P]-

1269 [ReC24H22N02P]+

1270 ReC24H2503

1271 ReC24H2504

1272 ReC26H2s04

1273 [ ReC31H28N02P]+

1274 ReC31H44P3

1275 ReC44H39C103P3

Derails ReJ Struclure

180 917

918

919

920

921

922

923

924

924,925

220

223

200

115

920

926

927

926

928

929

930

931

932

932

930

930

933

934

935

936

937

933

933

938

939

940

941


No. Formula Sfrucrure Derails

1276 [ ReC53H50C1NP4 1’ [ReC1(CNH2) (d~pe)~l[BF~l .Sv

1277 [ReC61H57C1P4 I+ 1278 ReSiC14H23N03P

1279 ReSiC19H33N03P Re(C(OSiMe3)=PBut} (CO) (NO) (cp*) 118

trans- [ ReCl ( 112-CH2CBz ) (dppe ) 1 [ BF4 I . Sv Re{ C( OSiMe3 )=PBut ] ( CO) (NO) ( Cp)

1286 Re2C40H5204

1287 [ Re2C49H47N202P2S I+ 1288 Re2C51H44C140P4

1289 Re2C60H53C14NOP4

1290 [Re2C65H72C13N3P4 I+ 1291 Re2SeC24H3004

1292 Re2Sn2C24H3609

1293 Re2TiC32H34010

1294 ! Re3C12H13NO10 1-

1295 [ Re3C14H9N09 1-

1296 [Re3Cl5Ol5S1+

1297 Re3Cl8H7OI3

1298 [Re3C27H190gP]-

1299 [ Re3C46H32010P2 1- 1300 [Re3TeC15015]+

1301 [Re4Cl4H5Ol41-

1302 [RhC7H14N2 1’

1303 [RhC8H12C12]-

1304 [RhCsHleN2 I +

1305 RhCgH27013P4 CO I P( W e 1 201 { P( OMe 1 20Hl 153

1306 RhC10H25C13N02 RhC13(CH2CH=NEt2) (DMs0l2 - 1307 RhC11H15N20 Rh( CM(leQI2CH2NM“ ( CO) ( ($1

Ref.

942

94 3

944

944

945

945

945

542

768

946

947

948

949

949

950

951

952

953

954

955

132

956

955

957

132

958

959

960

959

961

962

963

Structures determined by Diflraction Methods 469

No.

1308

1309

1310

1311

1312

1313

1314

1315

1316

1317

1318

1319

1320

1321

1322

1323

1324

1325

1326

1327

1328

1329

1330

1331

1332

1333

1334

1335

1336

1337

1338

1339

Fomla

Rhc12H1502

RhC13H14C1303

RhC13H15 [ *c14H10N602 1'

RhC15H9N202 [*c16H16 1'

Rhc17H16N3

*c18H1 3'lN02 [*cigH25N]+

RhC21H24F8P

RhC21H25N2

*c25H20N203P [ mc25H40NP 1 +

RhC27H18BrF4N02P

RhC27H25F303P

RhC27H34C13N4P2

*'2eH36' [ RhC29H45C1NP 1'

RhC30H37F302P

Rhc33H40P

RhC37H2 5'2

*C37H670P2 [*C40H34P2S I+ [*C&8P2S2 1'

*c42H4804P3

RhC42H7303P2 RhC45H31BrF4NOP2

[*C45H40P2 1'

*c50H39C1F12P3S2

[*C50H39F12P3S2 I + [RhRuC5&7C1Pq 1'

-C58H57P4

Stmmn Dem'ls Rqf.

247

964

966

967

968

210

971

972

973

974

975

976

977

978

979

978

56 5

980

981

982

983

984

985

986

987

988

988

989

990

470

No.

1340

1341

1342

1343

1344

1345

1346

1347

1348

1349

1350

1351

1352

1353

1354

1355

1356

1357

1358

1359

1360

1361

1362

1363

1364

1365

1366

1367

1368

1369

1370

1371

Formula

RhSb3C57H4802 RhTiC20H27

Rhwc44H3 5'3'2

RhZrC43H37P2

Rh2C16H12F8

Rh2C16H24C12 m2C16H3802Pg 1 2+

Rh2C17H1 3'gN

Rh2C18H10N206

Rh2c18H18

Rh2C19H16F60

*2C20H21 1 +

Rh2C20H3604P2

Rh2C21H20F602

Rh2C22H18C12N402S4 [ Rh2C22H3002 1 2-

[ Rh2C24H34C12N2 1 2+

Rh2C24H38C1P

*2C25H2 4C12F4N2

Rh2C28H400 [ Rh2C30H42N202 1 2+

[ 1 2+

Rh2C34H20F8N2S2

Rh2C35H28C13N304P2

Rh2C36H48

Rh2C38H8 5'2'3

Rh2C40H5002P2 [ Rh2c4oH64p4 1 2+

Rh2C42H28Br2F806P2 [ Rh2C44H47N40P2 I +

*2C46H4802P2S2

Rh2C57H9903P3

Structure

Rh( COMe 1 (CO) ( SbPh3 )


Derails Ref.

991

992

124

993

994

316

995

994

996

386

997

386

998

997

999

1000

1001

56

1002

1003

1004

1005

1006

1007

1008

56

1009

1010

1011

1012

1013

981

Structures determined by Diffraction Methods 47 1

No. Formula

1372 [Rh2C5gH46IN20??4 1' 1373 Rh2C62HglNS4

1374 [Rh2C74H80N4P4 12'

1375 Rh2Ru2C12H2012

1376 Rh2Ru2C29H17011P

1377 Rh2Se5C20H30

1378 Rh2WC16H24Sq

1379 Rh2ZrC46H5202P2S2

1380 Rh3C12H12C12N304

1381 [ Rh3C16H8N206S2]+

1382 Rh3C18H8c12FqN304

1383 Rh3C24H36Ng

1384 Rh3C29H5405P3

1385 ~~3C34H34N404 1' 1386 [ Rh3C66H60C1202P6]+

1387 [ Rh3C72H6qC1206P6 1'

1388 Rh4C26H12Cl4N2O8

1389 [ RhqC58H84Ne06P2 1 2+

1390 Rh6CqOH7408P4

1391 [ Rh10C21021 1 2-

1392 I Rh12C23HN2023 1 3- 1393 [ RuC7H21N504 1 2+

1394 RuC10H12C120

1395 RuC13H10C14N302P3

1396 [RuCl3Hl5]+

1397 RuC13H320P4

1398 RuC15H1803S

1399 RuCl6HI60

1400 RuC16H2002S2

1401 RuC16HZOS4

1402 RuC17H260P2

1403 [ RuC17H28C1N40]+

472

No. Formula

1404 [

1405 RuClgH29011P

1406 RuC20H2012N202

1407

1408 R u C ~ ~ H ~ ~

1409 RuCZ1H17Br

1410 [RuCzlHl7N4O

1411 RuC22H3304P

1412 RuC24H20C10P

1413 RuC28H36

1414 [RuC32H3002P

1415 [ R u C ~ ~ H ~ ~ P ] +

1416 [RuC35H35P2]+

1417 RuC36H3503P

1418 RuC37H3504P

1419 RuC38H30N4S2

1420 RUC38H31C1N4S2

1421 RuC38H40P2

1423 RuC39H33C103P2

1424 RuC39H34P2

1425 [ R u C ~ ~ H ~ ~ N ~ O P ~ ] +

1426 RuC41H38P2

1427 [RuC41H410P2 1' 1428 [RuC43H39P2]+

1429 RuC44H4008P2

1430 [ RuC44H42N30P2]+

1431 [ R U C ~ ~ H ~ ~ O P ~ ] +

1432 [

1433 RuC49H39N302P2

1434 [ RuC50H43P2 1' 1435 RuC51H41C10P2

1436 RuC51H4608P2S2

Organ ome tallic Chemistry

Rel.

1040

1041

1042

1043

781

1044

1045

1046

1047

1048

1049

1050

1051

1052

1052

1053

1053

1054

1055

1056

1057

1058

1051

1059

1060

1061

1056

1062

1063

1056

1064

1065


No.

1437

1438

1439

1440

1441

1442

1443

1444

1445

1446

1447

1448

1449

1450

1451

1452

1453

1454

1455

1456

1457

1458

1459

1460

1461

1462

1463

1464

1465

1466

1467

1468

473

Delails R d .

1066

1067

1068

1069

223 392

1070

1071

1072

1073

1072

1074

1072

325,1075

1076

1077

1078

1079

1080

270 792

412

1081

1074

1082

1076

1055

1083

1084

278 1085

474

No.

1469

1470

1471

1472

1473

1474

1475

1476

1477

1478

1479

1480

1481

1482

1483

1484

1485

1486

1487

1488

1489

1490

1491

1492

1493

1494

1495

1496

1497

1498

1499

1500

Formula

R'2Si6C24H66

R'2si 6C24H6602

Ru3C12H14N208S2

m3C14H19N308S2

R'3c1 5H2F6N201 0

R'3c1 5H1 lN09

m3C16H9m11

m3C17H11N01 0

R'3C19H11N07

m3C20H8N2010

Ru3C20H10C12N208

R'3C23H9N010

R'3C27H14N01 0'

m3C27H2008P2

m3C33H2407P2S

Ru3c3 4H20C12N209P2

m3C35H2608P2

R'3C36H3207P2S

R'3C37H3208P2S

R'3C44H29N09P2

R'3C44H30C1208P2

m3C44H32N207P2

RU3C52H4408P4

[RU3C55H46106P4 1'

R'3C55H4606P4

'm4c12H3012 I-

R'4c1401 3

R'4C2 5HllNOll

R'4c2 5H1 2'1 1'2

R'4C26H2209P2S2

R'4C29H20010P2

m4C35H26010P2


Strucntre Defoifs

255

130

179

121

118

Re/.

792

792

1088

1088

1089

1090

804

1091

1092

1089

1093

1094

1095

811

1096

1097

1082

1098

1098

1095

1099

1100

1101

1102

1102

820

1103

1104

1105

1106

811

1107


No. Fotmula

1501 R'4C35H26011P2

1502 R'4C38H20012P2

1503 R'4C38H56020 1504 &5C26H11013P

1505 m5C39H20N201 3 1506 Ru5C44H27N2014P

1507 Ru5C45H25N2012P

1508 R'5C45H26013P2

1509 R'6C36H20012P4

l5l0 R'6C42H25012P5 1511 &8C24H8017S2

1512 Ru8C26H7019P

1513 SbCloH1102S2

1514 [ SbC12Hlo]-

1515 SbCZ1H16NS

1516 SbC21H210s

1517 SbC24H200PS

1518 SbC24H2002P

1519 SbC24H20PS2

1520 SbC30H2506S2

1521 SbSi2W2C17H19010

1522 Sb2C4H12

1523 Sb2C36H3002

1524 Sb2C38H30F6O7S2

1525 Sb2C48Hq007S2

1526 [ Sb3C24H20]-

1527 [ Sb4C24H201g 1-

1528 Sb4C48H4006

1529 Sb6C36H30

1530 SeC11H11F3S2

1531 SeCl lH1 40S2

1532 SeC14H9C1

Ru8P( CO) 17 ( P - C ~ ) (P-? : n6-B2 1 . Sv

SbPh ( SOCMe )

[ Li ( 12-c-4 l2 1 [ SbPh2 I . Sv

SbPh2(SC9H6N)

p4-N2CPh2).SV

CCPh ) . Sv

2

130

E

130

1110

1111

1112

1112

1113

1114

1115

39

1116

1117

1118

1118

41

177

181

1119

1117

1120

1120

39

1121

1117

1122

1123

1123

1124

476

No. Formula

1533 SeC24H28N6

1534 SeC32H250P

1535 SeSiC7H1702P

1536 SeWC24H2005

1537 Se2C10H1204

1538 Se2C12F8

1539 Se2C12H8N204

1540 Se2C16H1604

1541 Se2C34H24

1542 Se2SiC26H22

1543 [ Se3C3H9]+

1544 Se4C10H12

1545 [ Se4TeC12H8N8]2+

1546 Se4TeC12H24N6

1547 [ Se4W2C10010 12+ 1548 Se5V2C12H14

1549 Se8C10H8

1550 SiC3H7N0

1551 SiC3H7NS

1552 SiC5H15N

1553 SiC5H15NS2

1554 SiC6H1602

1555 [ SiCloH23N203 I +

1556 SiC12H2402

1557 SiC14H26N204

1558 SiC18H19N

1559 SiC18H20N204

1560 SiC20H1802

1561 SiC20H23N

1562 SiC20H30

1563 SiC25H25N

1564 SiC29H39N2P


SImcntre Derails

187

170

R d .

1125

1126

1127

1128

1129

1130

1131

1132

1133

490

1134

[(TMSF)2]X (X=BF4,PFd) N at 4,20;X at hp 1135,1136 -

I i (CH2)2Se2]2TSeFlX tX+uI3r2,PF6)

S i HMe 2NC0

SiHMe2NCS

3 Me2NS iMe

Me3SiN(SO2MeI2

Pri2Si(OHI2

[ iiN( CH2CH2b 1 3CH2NMe3 1 I

SiW2 ( OH 1

s'iH2Ph(C,,H,dMe,-1,8)

Ph2SiC4H4Me2(N02)2

5 1,3-dioxa-2-silacycloalkanes

OC6H10NCHMeSiN(CH2CH20)3 m

$iHMePh( Cl0H8CH2he2-1, 8 ) 5 Si(rl -Cp*)2

- E-SiPh3CH=cBu(CN)

Ph3Si!hut ( CH2 ) 3hut

1137

1137

1138

1139

1140,1141

E 1142

E 1142

E,X at 116 1143

1144

1145

1146

1147

1148

1149

1150

1151

1149

1152

1153

1154


No. Fonnula Stmcwe Details

1565 SiSnClgH2eBrN dn(CH(SiMe3)C6H4&e2]BrMePh

1566 SiSnC29H41N2P Sn(CH2PPh3) ( (NBut),SiMe2}

1567 SiTaC13H2p3 TaC13 ( SiMe3 ) (Cp* )

1568 SiTaC16H33C12P TaC12(SiMe3)(PMe3)(Cp*)

1569 SiTaC19HZ9C13N0 TaC13( 02-OCpySiMe3) (Cp*)

1570 SiTiC15H25C1P TiCl( PMe2SiMe3 ) ( Cp) 180

1571 SiTiC26H350P

1572 SiTi2C26H28 {Ti ( Cp) 1 ( P-H) ( P-HSiHPh 1 'low T'

1573 SiWC28H25N04 W(C(NC5Hlo 1 SiPh3 1 (CO)

1575 SiW2C23H24C18N2 {WCl,(py) I,( t12:t12'-PhCeCCSSiMe3) 1576 SiZrClgH24C1N z!C1(CHSiMe3C5H4&-2)(CP)Z

Ti(PMe3) { Q2+C-CPhC(SiMe3)=cH2) (Cp)

1574 SiW2C18H1406 w2 ( co) 6 { 0': 05'-( C5H4 ) 2SiMe2

411

Ref.

1155

1156

1157

1157

1158

1159

1160

1161

1162

1163

1164

1165

1577 SiZrC28H29C1

1578 SiZrC32H34C1P

1579 Si2C16HZ00q

1580 Si2C18H36N20

1581 Si2C18H41N0

1582 Si2C20H45N

1583 [Si2C20H48N2]2+

1584 Si2C24H220

1585 Si2C24H2203

1586 Si2C24H54

Z r C1( CHSiMe3 ( Cl4H9-9 ) } ( Cp )

ZrC1(CHSiMe3C6HqPPh2-o)(Cp)2

Me2Si(oC6H4C-c)2SiMe2

(N( CH2cH2cH2 1 3si 1 2~ But3SiN=SiMe2( THF)

But3SiN=SiBut2

[ P ~ ~ ~ s ~ N H B ~ ~ s ~ P ~ ~ ~ ~ ~ ~ J [ ( A ~ c ~ ~ ) ~ o I ( SiHPh2 ) 2O

I Si (OH )Ph2 1 20

Si2But6

1589 SizC26H4002

1590 Si2C26H54N2

1591 Si2C30H26

1592 Si2C32H380

1593 Si2C32H380

1594 Si2C36H20FloN2

1595 Si2C36H300

1596 Si2C36H3002

trans-{ SiBut ( Mes ( p-0) )

But2Si ( CBut-N) 2SiBut2

Me2Si2( 5,10-C14H10 l2

( Ph2ButSi ) 2O

Ph3SiM( cH2But ) SiMePhOMe

(Ph2SiNC6F5)2.4PhH

(Ph3Si)20.2PhH & .2picoline

Ph3SioOSiPh3

1165

1165

1166

1167

238 1168

1168

1169

1170

1171

1172

1173

1174

230 1175

1176

1177

1178

1179

1180

150 1181

1182

478

No.

1597

1598

1599

1600

1601

1602

1603

1604

1605

1606

1607

1608

1609

1610

1611

1612

1613

1614

1615

1616

1617

1618

1619

1620

1621

1622

1623

1624

1625

1626

1627


Stmrlure Derails ReJ.

(Me~)~HSisiF~(C~H~Bu~~-2,4,6) 1183

{Si(Mes)2(p-O))2.PhNe 230 1175

TaCl (dmpe ) ( n2-Me3SioCCOSiMe3 ) 1184

{Ti (Cp 1 (lu-HSiHPh 1 1 1161

V{ (Buh) 2SiMe2} 508

h(CHSiMe3CHSiMe3h2) (NC6H3Pr12-2,6)-

[ m e ( CF3 12 12 253 1185

IW(NsiMe3)(C~)(p-S))2 1186

W SiMe3 12( Cp* l 2 98 1187

YCH(SiMe3)2(Cp*)2 108 1187

1188 [ Yb( P-C~ 1 In: O'-( C5H4 I2SiMe2) l 2 Zn( r11-C5H4SiMe3 1 ( n5-C5H4SiMe3) E 1189

Si3But612 1190

P7( SiPh3) 3. 2PhH 503

1191

V(NBut) (SSiPh3)3.Sv 1192

Me2Si(02SiMe2)2SiMeCH2P3N3C14Me 1193

(Me3Si)2C(SiMe20H)2 1147

But2Si ( OSiMe20) 2SiBut2 1194

( But2SiOSiMe3NH) 1194

Pri2Si (NHsiPri2m)siPri2 1194

(SiMe3)2CHPhC=C(CHPhSiMe3)SiH(OMe)2 1195

(Ph2Si02)2Si2Me2C2H4 153 1196

Si2Me4 { SSi ( OBut) 3) 1197

{Ph2SiOSiMe(CHCH2)O)2 153 1198

Cb2CMeCMeCH2&C(CHPhSiMe3)CPh&SiMej)2 1195

U( CNEt 1 ( n-C5H4SiMe3 1

Si4 ( rn2But) 1199

ButZSi2 {psi ( C6H3Et2-2, 6 ) 2}2 1200

SnICH(SiMe3)212 494

ZL{NC~H,&S~M~,),-~)~ 184

zr( CH2SiMe3 1 (dmpe 1 1201

(SiMe3 1 5P2 (PHI 1202


No. Formula

1628 Si5C28H46

1629 Si5C30H7206S2

1630 Si6C30H58N202

1631 Si6Ta2C74H16206

1632 Si6ThC33H63

1633 Si6Zn2C50H6802

1634 Si7ZrC52H92012

1635 Si8C12H36010

1636 Si8C16H46C14N308P3

1637 Si8C16H4608

1638 Si8C36H9006S2

1639 Si8Sn2C28H76

1640 Si8U2Cq4Hs4X2

1641 Si13C26H78

1642 %i16C32Hg6

1643 SmC20H30

1644 SmC24H380X

1645 Sm.$52H70N2

16 46 S%Cs4H7 oN202

1647 Sm2C56H7002

1648 SnCH313

1649 SnC2H5C13

1650 SnC4H1012

1651 SnC6HI1Cl3O2

1652 SnC9H18N203S

1653 SnC10H1403

1654 SnC10H21N

1655 SnC10H2202

1656 SnC11H1603

1657 SnC12Hz2X2

16 58 SnCl 2H26N2S4

1659 [SnC12Hj102]+

stmcture Details Ref.

o=C6H4Si(SiMe3)C{CPhC(SiMe3)2)CSiMe3 1203

Si3Me6{ SSi ( OBut } 1197

~is-[Si(Mes){N(SiMe~)~](,v-O) l 2 250 1175

I 1

-

{ (Me2PhSi)3CZn(,v-OH)}2

(Cp* )ZrSi7Q7(p-0) 12

dispiro[5.3.5.31-Me12Si8010

540

1206

1207

{Me2Si(02SiMe2)2SiMeCH2}2P3N3C14 1193

(Me7Si404 12C2H4 153 1196

Si6Me12{SSi(OBut)3]2 1197

1 Sn( CH ( SiMe3 1 1 1 498

[LJ{ rt-C5H3 ( SiMe3 1 2-1, 3 I ( 1 ~ x 1 I 1208 (X=Cl ,Br 1

193 1209

198 1209

1213

1214

1215

1216

1217

Me2Sn{02CCH(CH2CH2SMe)NCOCH2NH2} 1218

1219

1220

1221

1219

SnX2Cy2 ( X=Br , C1) 1222

1223

1224

480 Organomeiallic Chemistry

No. Fonnulu

1660 SnC14H3004P2S4

1661 SnC14H4113N602P2

1662 SnC15H26C1P

1663 SnC16H19C12N02

1664 SnC16H33N30P2S2

1665 SnC18H15C1

1666 SnC22H220S2

1667 SnC24H22C12N2

1668 SnC25HlgC102

1669 SnC25H20N202S

1670 SnC28H41N02

1671 SnC30H28BrN0

1672 SnC37H32N208P2

1673 SnC37H42NPS

1674 SnC38H4004

1675 SnC50H42P4

1676 SnC80H,0

1677 SnTaC11H15C12

1678 SnUC33H30

1679 Sn2C4H12C12

1680 Sn2C,H1803

1681 Sn2C24H48S8

1682 Sn2C38H30P2

1683 Sn2Ti C42H54C1N02

1684 [ Sn3C6H18C18 ] 2-

1685 Sn3C54H45P7

1686 SnqC16H36010

1687 Sn4C32H72

1688 Sn4CqOHs8

1689 TaC13H1507

1690 TaC26H#

1691 TaC26H30N

S1ruc:ure

SWe2 I: SP ( S 1 02C2Me4 1

sn( C H ~ C H ~ M ~ P P ~ B ~ ~ )ClMe2

Sn13Et(13MPA)2 - SnCl2Me2(N-salicy1idene-panisidine)

Details Ref.

1225

1226

1227

1228

1229

110 1230

1231

1232

1233

1234

150 1235

1236

57

1237

1238

837

138 489

1239

1240

113 1241

1242

112 1243

1156

233 1244

1245

503

1246

185 1247

1241

1248

1249

1249


No. Fonnula

1692 TaC31H5102

1693 TaC33H5504

1694 TaC49Hgg03

1695 TcC15H27Br2N40

1696 TeC14H18C1203

1697 TeCl 5H11B r 3O

1698 TeC15H15N3S2

1699 TeC18H15F3

1700 [ TeC21H30Br2N1+

1701 Te2C6HI2N2O2

1702 Te2C12H3012

1703 Te2C24H32N2

1704 Te2Ti2C36H48F1002

1705 Te2Zr2C36H52

1706 Te3C22H16N2

1707 Te4C12H12

1708 Te4C24H60C14

1709 ThC20H30S5

1710 ThC24H36

1711 ThC30H52

1712 ThC36H36

1713 ThC44H50P2

1714 TiC7H12C12N2

1715 TiC7H19C13P2

1716 TiC8H21C13P2

1717 [TiCgH5O4]-

1718 TiCloHloN2S3

1719 TiC10H10N4S3

1720 TiC11H10C12N2

1721 TiCllH12C12N2

1722 TiC14H23C12N

1723 TiC16H19N0

48 1

Details Re&

108 1250

114 1250

1251

280 1252

1253

1254

1255

1256

1257

168 1258

1259

526

143 1260

1261

1262

1263,1264

1259

1265

1266

N at 50 1267

1268

178 1269

218 1270

X,N at 20 1271

1271

1272

1273

1273

1274

231 1270

238 1214

1275


No. Formula

1724 TiC17H13N04

1725 TiC17H17N402

1727 TiC20H18N2 1 2+ 1728 TiC20H32S2

1729 [TiC22H18N2 I 2+

1730 TiC23H20C12NP

1726 TiCl9H16O2

1731 TiC23H27NOS

1732 [TiC23H37C1NOl+

1733 TiC24H2004

1734 TiC26H2804P2S4

1735 TiC26H29N2P

1736 [TiC26Hd4N2O2 12+ 1737 TiC2?H2?N4

1738 TiC31H36

1739 TiC35H31P

1740 Ti2C20H200

1741 Ti2C24H32P2

1742 Ti2C26H30C14N6P2

1743 Ti2C26H36P2

1744 Ti2C28H2804

1745 Ti2C34H30C12N4

1746 [ Ti3C18H21010 1' 1747 [Ti3C21H33071+

1748 Ti3C33H5403

1749 Ti3C35H32C1N402

1750 Ti4C24H2802S8

1751 Ti 6C30H30C1206

1752 Ti6C36H42C1404

1753 T1C5H5

1754 T1C17H19N404

1755 T1C27H27N40S

stmcture Details Ref.

Ti(dipicolinate1 (Cp), 243 1276

Ti(theophyllinato)(Cp)2 173 1277

k (CPh=CH&) (Cp) .PhC&C02H 1278

(Ti(C~)~(bim) I[tfo12 1279

1280

1279

TiC12(NPPh3) (Cp) .Sv 223 1274

Ti (NCS ) ( OXy ) ( Cp) ( n-C5H3MePc1 )

[TiC1(DMF)(Cp*)21[tfo]

1281

1282

1284

1285

1300

1301

1302

1303

Structures determined by Diflraction Methods

No.

1756

1757

1758

1759

1760

1761

1762

1763

1764

1765

1766

1767

1768

1769

1770

1771

1772

1773

1774

1775

1776

1777

1778

1779

1780

1781

1782

1783

1784

1785

1786

1787

483

Details Ref.

1304

1305

1302

1302

321

1306

1307

1308

1309

1309

1310

1306

1308

1311

1310

1312

163 1313

1314

1315

1315

1315

1316

278


No. Formula

1788 [ WC2C17 1-

1789 [WC2F5I2I2-

1790 [WC4Br304 1-

1791 WC9H8103P

1792 WC10H5N05

1793 WC10H5N05S

1794 [ WC12H12103 I+

1795 WC13H13N03

1796 WC15H2302P

1797 WC16H8N204

1798 WC16H22NogP

1799 WC17H17N05

1800 WC17H2806

1801 WCl8HlOBrNO4

1802 WC18H30

1803 WC19H26N202S4

180 4 WC20H1 5N05

1805 WC21H4203P2

1806 WC22H25N02

1807 WC23H17N503

1808 WC24H30N2S4

1809 WC27H2302P

1810 WC27H34C12P2

1811 WC28H30C120P

1812 WC30H30N2S4

1813 [WC32H3203P]+

1814 WC35H25N06P2

1815 WC36H57N2P3

1816 WC39H3403P2

1817 WC39H6603P2

1818 [W2C61506]-

1819 W2C10H12N202

Derails ReJ.

1322

1323

238 1324

1325

1326

1327

644

666

1328

1329

301

1330

1331

233 1332

676

1333

1330

1334

1335

684

1336

1337

1338

1339

1340

1341

1342

1343

1337

1334

644

1344

485 Structures determined by Diyraction Methods

No, Foornwla

1820 W2C14H38C13N3P2

1821 W2C16H20O8P2

1822 W2Cl7H6Ol0

1823 W2C18H28C14N4

1824 W2C20H36C12N6

1825 W2C20H4604

1826 W2C24H34C13N5

1827 W2CZ4Hq2C13N3P2

1828 W2C26H48N2

1829 W2C28H4gN4

1830 W2C28H52

1831 W2C#66N206

1832 W2C29H6007

1833 W2C31H2404

1834 W2C32H42N8

1835 W2C32H66N2O8

1836 W2C36H50N8

1837 w2c41H8lm6

1838 W2C42H78N206

l8 39 '3'21H1 0'1 5'2 1840 YC24H38C10

1841 Y2C28H3402

1842 Y5C33H4909

1843 YbC15H210

1844 Ybc2OH30

1845 ZnC20H30

1846 ZrC12H15C10

1847 ZrC13H16C1m2

1848 ZrC14H1904P

1849 [ ZrC15H2101+

1850 ( ZrC17H2105S I +

1851 ZrC18H24

E 183

E 1189

1361

140 1362

1363

1364

1365

210 1366


No. Formula Struciure Details Rej.

1852 ZrC18H26C12 ZrC12 ( Q-C~H~BU~) 1367

1853 ZrC19H23P 118

1855 ZrC21H28

1854 ZrC19H27P Zr(PMe3) (n2-cyclohexyne) (Cp),

Zr ( n3-C3H5 ) ( Q4-COt) ( Cp* ) 210

1856 ZrC22H26N2 Zr ( NC4H2Me2 1 ( Cp 1

1857 ZrC24H23C10

1858 ZrC24H24N202 ZrBz(ONBzNO)(Cp)2

1859 ZrC24H2406S2 Zr (($1 (03S( pol 1 1 1860 ZrC32H52N4

1861 [ Zr2C10H2408 I 4+ [ IZr(H20)3(Cp)(~-oH)~21X4 (XEtfo,clo4) 173

1862 Zr2C20H18C120

1863 Zr2C20H20S2 I Zr ( CP) (P-S 1 1 1864 Zr2C25H28C12

1865 Zr2C38H40N4 (Zr(Cp' )2](~-NNCHPh)(Q1:n2-NNCHPh) .Sv

1866 Zr2C40H24

1867 Zr2C46H4002

1869 [ Zr3C36H33010 1'

2 rC1( Q2-Ph2COMe ) ( Cp )

Z'r i mutdCH2NBut6 ( mut &ut 1 ( cp '

{zrc1( cp) 1 ( p a ) ( n5: n5,-fulvene

( Cp)2C1Zr{ n2H-MeC=CHZrC1 (Cp' )2}

{zr ( Cp' ) ( n1 : n2-CCPh) } {zr (Cp) (~-n'O-mPh~ 1 1

1868 Zr2C54H6002 (zr ( Q8-cot 1 ( P - 0 , Q 2 -OCM~S~ 1 I [ IZr(Cp) (P-OH) (~-0~Cph) 13(~34) 1 [PhCO21 .Sv

Addiriorral abbrevhiom used in Main T&Ie

18-c-6 18-crown-6 (etc. for others) bim2 2,2'-bi-imidazole

cyclenPH cyclenphosphorane DBmF bibenzotetrathiofulvalene detc diethydithiocarbamate DMm Me02CC=CC02Me dmpn (Me2PI2CH2 dmpz 3,5-dimethylpyrazol-l-yl

d p m p P ~ P ( CH2PPh2 1 2 HDBT dibenzoyltartrateH ind indenyl K-2.2.1 4,7,13,16,21-pentaoxa-l,lO~iazabicyclo[8.8.5ltricos~e MeUc l-methyluracil anion napy 1,8-naphthyridine nP3 N( CH2CH2Ph2 I 3 oTol Ftolyl oxine 8-oxoquinolate pTol ptolyl sv solvated crystal tdt isotrithionedithiolate tfb 5,6,7,8-tetrafluorobarrelene TMSA N(SiMe3)2- TMSF tetramethyltetraselenofulvalene tripod HC(PPh2)3 TSeF tetraselenofulvalene tz triazolate XY 2,6-Me2C6H4

5 Cp' Q5-C5H4Me CP* n -C5Me5

dmtc dimethyldithiocarbamate dppnPa PhAs ( CH2PPh2 1 2

1368

1369

1370

1371

1372

1373

1365

1374

1375

1376

1280

1377

1378

1379

1380

1381

1382


3 Metals Cross Reference Table ---

A list of mixed metal compound numbers which are listed alphabetically in the Main Table under another metal.

Meld

As Au B co Cr cu Fe

Ga Ge H9 I r Li LU

2 MO

Nb Ni 0s

Pb Pd Pr Pt

Re Rh

Ru

Sb Se

Si

Sm Sn

Ta Te

Compound Numbers

4 4, 12, 13, 41 27, 28, 29, 33, 95, 96, 121, 122 42, 43, 44, 45, 53, 54, 97, 98, 145, 215, 216, 228, 229, 230, 231, 239 44, 54, 55, 99, 146, 288 354 42, 43, 46, 55, 56, 97, 121, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 188, 189, 190, 205, 206, 224, 235, 236, 237, 239, 240,

398, 399, 400, 401, 402, 403, 404, 405, 418, 419, 448, 449 5, 57, 58, 59, 75, 82, 430, 431 208, 295, 369, 373, 406, 507, 508 509, 510 60, 61, 78, 123, 290, 511, 691, 699 47, 62, 63, 159, 160, 161, 191, 200, 245, 659, 744, 747 802 296 , 297 298, 299, 300, 333, 356, 357, 432, 512, 631, 632, 646, 651 42, 43, 64, 65, 80, 81, 100, 162, 163, 164, 165, 166, 167, 168, 192, 217, 301, 302, 303, 304, 358, 420, 431, 433, 513, 514, 515, 516, 517, 518, 519, 520, 600, 601, 654, 660, 661, 774, 792, 846, 847 124, 748 66, 76, 193, 204, 207, 291, 292, 305, 306, 307, 334, 602, 803 6, 67, 101, 102, 103, 104, 105, 106, 107, 305, 434, 435, 722, 945, 1001, 1027, 1028 647 48, 218, 521, 946, 947, 948 1007 7, 8, 14, 68, 125, 131, 209, 210, 219, 220, 225, 522, 523, 524, 692, 723, 848, 949, 1040, 1041, 1048, 1067, 1102, 1103, 1118, 1119, 1122, 1123, 1134, 1135, 1164, 1165, 1179 108, 109, 169, 400, 662, 671, 849, 850, 950, 951, 1104, 1225 9, 10, 60, 69, 79, 127, 153, 170, 221, 222, 226, 293, 308, 309, 335, 336, 337, 525, 526, 527, 528, 529, 603, 633, 634, 635, 636, 660, 663, 664, 775, 952, 953, 1046, 1068, 1226 11, 15, 98, 110, 126, 171, 211, 290, 293, 306, 310, 311, 312, 313, 314, 332,

1042, 1166, 1227, 1338, 1339, 1375, 1376 49, 1228, 1340, 1468 172, 401, 407, 423, 424, 532, 684, 692, 725, 793, 1029, 1167, 1180, 1229, 1291, 1377, 1438, 1439

200, 201, 202, 203, 208, 212, 213, 232, 244, 315, 316, 340, 408, 421, 508, 533, 534, 535, 536, 537, 605, 606, 607, 659, 685, 686, 687, 688, 689, 690,

805, 806, 807, 812, 813, 814, 815, 819, 820, 821, 828, 829, 833, 850, 851, 852, 853, 854, 954, 955, 956, 957, 958, 1011, 1030, 1069, 1070, 1105, 1167, 1181, 1278, 1279, 1440, 1441, 1469, 1470, 1521, 1535, 1542 34 70, 177, 202, 203, 538, 661, 872, 959, 960, 1013, 1014, 1106, 1107, 1292, 1565, 1566, 1624, 1639 1567, 1568, 1569, 1599, 1631, 1677 520, 600, 601, 637, 727, 873, 874, 1300, 1545, 1546

242, 289, 290, 291, 292, 293, 294, 329, 330, 3311 3321 355, 369, 396, 3971

335, 338, 339, 354, 359, 436, 437, 438, 447, 530, 531, 604, 648, 724, 134,

19, 20, 46, 59, 64, 82, 122, 124, 168, 173, 174, 175, 176, 194, 195, 196,

691, 693, 699, 700, 706, 726, 744, 747, 749, 776, 777, 778, 779, 780, 804,


Metal

Th Ti TI U v W

Y Yb Zn Zr

Metals Cross Reference Table (continued) ---- Comporcnd Numbers

1230, 1632

656 35, 1610, 1640, 1610

SO, 51, 71, 12, 13, 95, 96, 153, 154, 155, 156, 170, 178, 179, 196, 219, 220, 241, 313, 311, 310, 330, 339, 341, 342, 439, 532, 542, 543, 544, 545,

30, 31, 360, 806, 1293, 1341, 1570, 1571, 1572, 1600, 1683, 1704

539, 540, 541, 008, 1031, 1548, 1601, 1611

546, 547, 548, 549, 550, 608, 609, 610, 611, 638, 649, 655, 608, 723, 781, 782, 783, 830, 1040, 1041, iioa, 1124, 1225, 1231, 1232, 1233, 1247, 1253, 1x4, 1256, 1200, 1281, 1282, 1342, 1na, 1521, 1536, 1547, 1573, 1574, 1575, 1602, 1603, 1764, 1765 1604, 1605 797, 1606 1607, 1625, 1633

1705 21, 22, 100, 551, 961, 962, 1343, 1379, 1442, 1576, 1517, m a , 1626, 1634,

Structures determined by Difiaction Methods 489

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38 39

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4 1

42 43

44 45

46 47

48

49

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51 52 53

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58 59 60 61

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64 65 66

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70 71

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74 75

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77 78

79 80

81

82 83

84

85

86

87

88 89

90

91

92 93

94 95 96

97

98

99

100 101 102

103

104 105

106

107

108

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108, 317. 269 J.P.Gilday and D.A.Widdawson, J. Chem. SOC., Chem. Conmnxn., 1986, 1235. 270 K.Angermund, A.Dbhring, P.W. JOTIY~K- C.C.Rani30, Organometallics,

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2244. 273 K.H.&tz, W.Kuhn, G.Miiller, B.Huber, H.G.ALt, Angew. Chem., Int. Ed. Engl.,

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249 R.B.King, W.-K.Fu, E.M.Holt, Inorg. Chem., 90.

Trans., 1986, 1141.


280

281 282 283

284

285

286

287

288 289

290 291

292

293

294 295

296 297 298 299

300 301 302

303 304 305

306

307

308

309

310 311

312

313

314

315

316

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318 319 320

321

322 323

324 325

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329 330 331 332

333 334

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336 337 3 38

339

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341

342

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344 345

346 347 348 349 350 351

352

353 354

355 356

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498

360 361 362

363

364 36 5 366

367

368

369

370

371 372 373

374

375

376 377

378 379

380 381 382 383 384

385

386

387

388 389 390 391

392 393

394 395 396

397

398 399

400

401


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5, 593.

Structures determined by Diflraction Methods 499

402 403

404

405

406

407 408 409

410

411 412

413 414 415

416

417

418

419

420

421 422 423

424 425 426

427

428 429 430

431

432 433

434

435

436

437 4 38 439 440

441

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c5.

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R.L.De and H.Vahrenkamp, Z. Naturforsch., 1986 I 4 m 273.

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442

443 444 445 446 447

448

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451 452 453 4 54 455 456

457

458 459 460

461 462 463

464 465

466 467 468

469

470

471 472

473 474 475 476

477 478 479 480 481

482 483 484 485

486 487

488 489

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Structures determined by Difraction Methods 50 1

490

491

492

493

494

495

496

497 498

499 500 501 502 503 504

505 506

507

508

509

510 511 512

51 3 514

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516

517

518 519

520 521 522

523

524

525 526

527

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1

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543 544

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568

569 57 0

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572

57 3 57 4 575 576

577

578

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580

58 1

582 58 3 584

585

586

587

588 589 590

591

592

59 3 59 4

59 5

596

597 598

599 600

601 602 603 604 605

606

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J.S.Ricci Jr., T.F.Koetzle, M.-J.Fernandez, P.M.Maitlis, J.C.Green, J-

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648

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658

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661

662 663

664

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Structures determined by Dtyraction Methods 507

727

728

729 730

731 732 733 734

735

736 737 738

739

740 741

742

743

744

745 746

747 748

749

750

751

752 753

7 54 755 7 56 7 57

7 58

759

760

761 762 763

764

765 766

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804

805

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Chim. Acta, 1986, 114, L17.

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806 807

808

809

810 811

812

813 814

815

816

817

818 819 820 821 822 823 824 825 826

827

828 829

830 831

832

833 834

835 8 36 837 8 38

839

840

841 842

843

844

845

846

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847 J.M.Wisner, T.J.Bartczak, J.A.Ibers, J.J.Low, W.A.Goddard 111, J. Am. Chem.

848 mociani, M.Sala, A.Po?o, G.Bombieri, Organometallics, 1986, 5, 1369. 849 C.Arlen, M.Pfeffer, O.Bars, G.Le Borgne, J. Chem. SOC., Dalton Trans., 1986,

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1986, 1710. 857 J.Fornies, F.Martinez, R.Navarro, A.Redondo, M.Tomas, A.J.Welch, J-

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233. 883 A.G.Thayer and N.C.Payne, Acta C stallo r 1986, C42, 1302.

SOC. , 1986, 108, 347; Or anometallics, 1986, 5, 2044.

m t a , S.Sato, K.Kawazoe, C.Tamura, M.Sato, =a Crystallogr.,

514.

884 R.Us&, J. FOKni6SI H . T O 6 S X M W : K.Skkel, E.Kuwabara, Organometallics, 1986, 5, 1576.

Structures determined by Difraction Methods 51 1

885

886

887

888

889

890

891

892 893

894

895

896

897

898

899

900

901

902

903

904

905

906 907

908

909

910

911

912

913

914 915

916 917 918 919 920

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J.H.Davis Jr., P.G.Lenhert, C.M.Lukehart, L.A.Sacksteder, =a Crystallogr., 1986, C42, 1133. D.Carmichae1, P.B.Hitchcock, J.F.Nixon, F.Mathey, A-Pidcock, J. Chem. SOC., Chem. Conunun., 1986, 762. ~.p.~ai!ii!i F.A.Cotton, L.R.Falvello, w.Schwotzer, Inorg. Chem., 1986, 25, 763. L.Mano jlovi&Muir, S.S.M.Ling, R. J.Puddephatt, J. Chem. SOC., Dalton Trans., 1986, 151. H.Sch&llhorn, U.Thewalt, B.Lippert, J. Chem. SOC., Chem. Comxmn., 1986, 258. S.Myrvold, O.A.Nassif, G. Semelhago, EW-r , m F F r ,= Chim. Acta, 1986, 117, 17. Y.Yamamoto, T.Hagiwara, H.Yamazaki, Inor Chim. Acta, 1986, 115, L35. W.Bensmann, D.Fenske, E.Matern, Z. M d r F A.R.Siedle, R.A.Newmark, W.B.Gle%on, J. Am. Chem. SOC., 1986, 108, 767. Y.Yamamoto and H.Yamazaki, J. Chem. SoE,xlton Trans., 1986, 677. G.P.Elliott, J.A.K.Haward, ~ M ~ I ~ r e ~ & i i i i ~ F . G . A . S t o n e , J. Chem. SOC., Dalton Trans., 1986, 2091.

418, 575.

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940 941

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946 947 948

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951

952 953

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956 957

958

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1057 1058 1059

1060 1061 1062

1063

1064 1065

1066 1067

1068 1069

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1106 1107 1108

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1110 1111 1112 1113 1 1 1 4

1115 1116 1117 1118

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---

Chem., 1986, 315, C51. ou, J.-J.BOMet, P.Fompeyrine, G.Lavigne, N.Lugan, F.Mansilla,

1986, C42, 1011.

1986, 315, 321.


1119

1120 1121

1122

1123

1124

1125

1126

1127

1128

1129 1130 1131 1132

1133

1134 1135

1136

1137 1138

1139

1140 1141 1142

1143

1144 1145

1146

1147

1148

1149

1150

1151 1152 1153

1154

1155

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m, C42, 1433.

T. J. Emge I H. H .Wan9 I M.A.Beno I J . ~ W ~ m i i - ~ g ~ m a i n I J. Am.

Trans., 1986, 859.

--

518

1156 1157 1158 1159 1160

1161 1162 1163 1164 1165

1166

1167

1168

1169

1170

1171

1172

1173

1174

1175

1176

1177

1178 1179

1180 1181 1182

1183

1184

1185 1186 1187

1188

1189

1190

1191 1192 1193

1194


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-

1195 M. ishi kawa ,Xugisawa; H .Ahnoto, K .Matsusaki , S . Kami tori, K. Hirotsu,

Structures determined by Diyraction Methods 519

1196

1197

1198

1199

1200

1201

1202

1203

1204

1205

1206 1207

1208

1209 1210

1211

1212 1213

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1218 1219

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1225 1226

1227

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1229

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-7

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M.E;Kamwaya and L.E.Kho0, J. Fiz. Malays., 1985, 6, 39 (Chem. Abs. 1986, 105:42973m). H.Weichmann, J.Meunier-Piret, M.van Meerssche, J- Organomet. Chem. , 1986, 309, 273.


1230 1231 1232 1233

1234 1235

1236

1237 1238 1239

1240

1241 1242 1243 1244

1245 1246 1247 1248

1249 1250

1251 1252

1253

1254 1255

1256 1257 1258 1259 1260 1261

1262

1263 1264

1265

1266

1267

1268

1269

1270

1271

1272 1273

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Correction to Table 3 of Previous Volume (15)

Unfortunately, Table 3 in Chapter 16 of the previous Volume (15) contains a large number of errors. The following Table is the corrected version.

3 Metals Cross Reference Table ---

A list of mixed metal compound numbers which are listed alphabetically in the Main Table of Chapter 16, Volume 15 under another metal.

Metal

As B co Cr cu Fe

Ge Hf Hg Ir Li Lu Mg Mn Mo

Nb Nd Ni

0s Pb

Pr Pt

Re Rh

w

Ru

Sb Se

Compound Numbers

5, 12 6, 49, 50, 51, 93 52, 68, 94, 95, 136, 154, 155, 171, 172, 183, 207, 208 53, 54, 55, 69, 137, 138, 139, 304, 305 126, 269, 270 56, 57, 70, 96, 97, 98, 99, 119, 140, 141, 173, 174, 175, 176, 177, 178, 179, 186, 190, 216, 217, 219, 271, 272, 273, 274, 275, 276, 277, 278, 279, 306, 307, 333, 394, 395, 396, 418, 436, 437, 446, 447, 451, 456, 457 272, 308, 333, 334, 348, 509 167 349, 350, 632 142, 168, 309, 452, 641 16, 22, 23, 448, 454, 458, 621 757 , 758 24, 455 54, 55, 58, 71, 72, 73, 310, 449, 510, 511, 512, 581, 582, 671, 696, 774 52, 57, 59, 60, 61, 69, 143, 144, 145, 156, 157, 158, 191, 192, 272, 307, 308, 311, 312, 438, 513, 514, 515, 516, 517, 518, 519, 583, 584, 622, 687, 697, 807, 808, 809, 828 810 759 62, 180, 181, 182, 184, 273, 313, 334, 335, 514, 520, 521, 522, 585, 586, 760, 893, 894 63, 74, 100, 101, 120, 121, 313, 979 829 75, 76, 136, 193, 194, 523, 524, 830 935 71 8, 9, 10, 13, 77, 18, 79, 172, 179, 181, 182, 587, 588, 811, 812, 1000, 1001, 1029, 1030, 1031, 1032, 1033, 1034, 1035, 1053, 1102 14, 102, 195, 314, 315, 642, 643, 644, 645, 646, 783, 784, 1126 11, 76, 77, 78, 79, 80, 81, 82, 85, 95, 196, 197, 198, 199, 200, 203, 204, 209, 210, 211, 212, 279, 316, 317, 525, 526, 527, 528, 589, 590, 623, 647, 648, 649, 813, 936, 937, 1010, 1103, 1127, 1128, 1149 64, 95, 103, 104, 105, 122, 123, 185, 201, 316, 318, 319, 320, 321, 322, 323, 336, 349, 529, 698, 749, 895, 1247, 1248, 1249, 1250, 1251, 1286, 1296, 1297 , 1298 418, 419, 420, 425, 426, 530, 531, 591, 592, 833, 933, 1011, 1287, 1333 158, 397, 421, 422, 509, 581, 582, 593, 679, 831, 1129, 1130, 1131, 1252, 1253, 1334


M d

Si

sm Sn

Ta Te Th Ti T1 U V W

Y Yb zn zr

Metals Cross Reference Table (continued) - - ~ -

Compound Numbers

25, 26, 35, 36, 65, 66, 03, 146, 147, 159, 160, 161, 162, 167, 103, 200, 324, 337, 344, 345, 351, 398, 399, 400, 401, 439, 531, 532, 591, 594, 624, 654, 656, 672, 677, 670, 608, 707, 726, 727, 720, 759, 761, 762, 767, 768, 769, 770, 775, 776, 777, 704, 705, 707, 014, 032, 034, 096, 097, 090, 099, 900, 920, 940, 955, 956, 900, 901, 991, 995, 1036, 1037, 1030, 1039, 1060, 1085, 1086, 1105, 1132, 1133, 1150, 1153, 1154, 1155, 1199, 1254, 1335, 1372, 1390, 1399, 1416 1470 139, 145, 163, 201, 202, 283, 696, 729, 901, 1038, 1039, 1086, 1105, 1133, 1134, 1150, 1155, 1176, 1177, 1254, 1208, 1446, 1505 1447 15, 402, 440, 515, 516, 519, 504, 929, 930, 1413, 1414, 1497 101, 100, 902, 1336 27, 37, 30, 161, 164, 441, 931, 934, 1337, 1440, 1449, 1450 154, 205, 655 169, 954, 1611 162, 284, 1415, 1451, 1452, 1503 67, 04, 96, 191, 192, 202, 206, 210, 304, 300, 315, 325, 330, 423, 442, 533, 534, 592, 595, 596, 673, 674, 730, 747, 010, 015, 902, 903, 954, 903, 1040, 1041, 1042, 1043, 1135, 1136, 1137, 1138, 1178, 1179, 1289, 1338, 1339, 1400, 1401, 1402, 1420, 1453, 1471, 1472, 1473, 1474, 1475, 1476, 1482, 1490, 1499, 1500, 1501, 1502, 1506, 1540, 1549, 1550, 1504, 1507, 1606, 1611 1477 36 346, 904, 992 148, 904, 905, 906, 985, 1340, 1341, 1454, 1455, 1456, 1457, 1470, 1670, 1679

Documents

Organometallic chemistry. : a review of the literature published during 1986