X-RAY STRUCTURAL STUDIES OF SOME GROUP VIIICOMPOUNDS WITH CATALYTIC IMPLICATIONS

ByDOUGLAS ALLEN SULLIVAN

A DISSERTATION PRESENTED TO THE GRADUATECOUNCIL OF THE UNIVERSITY OF FLORIDA

IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FORTHE DEGREE OF DOCTOR OF PHILOSOPHY

UNIVERSITY OF FLORIDA

1975

To Jeanie

ACKNOWLEDGEMErJTS

I sincerely thank Dr. Gus J. Palenik for his enthusi-

astic guidance throughout this work. I am deeply apprecia-

tive of the advice and instruction concerning crystallo-

graphic techniques given by Dr. M. Mathew and of the diligent

synthetic work of Ruth C. Palenik. I wish to thank Dr.

Marvin Rausch for providing excellent samples of metallo-

cycle compounds. I am indebted to the chemistry faculties

of Marshall University and the University of Florida for

their apt instruction. I would like to especially thank the

other members of the Center for Molecular Structure for

their thoughtful suggestions and discussions. The typing

expertise of Ann Kennedy is evident in this, perhaps her

last, crystallographic dissertation. Lyle Plymale and Don

Herbert are acknowledged for their inspirational teaching

during my formative years. I would like to express my

appreciation to my parents, Mr. and Mrs. I. O. Sullivan, for

their support and encouragement throughout my formal educa-

tion. Finally, I thank my wife, Jeanie, and my son, David,

for their love and devoted understanding.

Ill

Table of Contents

ACKNOWLEDGEMENTS

LIST OF TABLES

LIST OF FIGURES

KEY TO ABBREVIATIONS

ABSTRACT

CHAPTER 1:

CHAPTER 2:

CHAPTER 3:

CHAPTER 4:

CHAPTER 5

CHAPTER 6

CHAPTER 7:

INTRODUCTION

SYNTHESES AND CHARACTERIZATION

X-RAY DIFFRACTION EXPERIMENTAL

AN INVESTIGATION OF LIGAND- INDUCEDPROTON SHIFT: THE CRYSTAL ANDMOLECULAR STRUCTURES OF TRANS -

CHLORO (DIMETHYLGLYOXIMATO) (DIMETHYL-GLYOXIME) (4-CHLOROANILINE) COBALT (III)DIHYDRATE, TRANS-CHLOROBIS (DIPHENYL-GLY0XIJ4AT0) ( 4-CHLOROANILINE) COBALT ( III)ETHANOLATE, AND TRANS-B IS (DIMETHYL-GLYOXIMATO) BIS (4-CHLOROANILINE) COBALT(III) CHLORIDE

A NOVEL BINUCLEATING LIGAND: THECRYSTAL AND MOLECULAR STRUCTURES OF1,4-DIHYDPJ^ZINOPHTHALAZINEBIS (2-PYRI-DINIUMCARBOXALDIMINE) NITRATE DIHYDRATEAND y-CHLOROTETRAAQUA [1 , 4-DIHYDRAZINO-PHTHALAZINE3IS ( 2-PYRIDINECARBOXALDIMINE)

]

DINICKEL(II) CHLORIDE DIHYDRATE

MODELS OF PROPOSED INTERMEDIATES FORTHE CATALYZED CYCLIZATION OF ACETYLENES:THE CRYSTAL AND MOLECULAR STRUCTURES OF1- (tt-CYCLOPENTADIENYL) -1-TRIPHENYLPHOS-PHINE-2, 3,4,5-TETRAKIS (PENTAFLUOROPHENYL)COBALTOLE and 1- (tt-CYCLOPENTADIENYL) -1-TRIPHENYLPHOSPHINE-2 ,3,4, 5-TETPAKIS(PENTAFLUOROPHENYL) RHODOLE

CONCLUDING REM^FJCS

111

vi

ix

X

xi

1

4

17

30

83

114

141

IV

APPENDIX A: BOOTHITl 144

APPENDIX B: OBSERVED AND CALCULATED STRUCTURE FACTORS 154

REFERENCES 230

BIOGRAPHICAL SKETCH 237

LIST OF TABLES

Table 1.

Table 2.

Table 3.

Table 4.

Table 5.

Table 6.

Table 7.

Table 8.

Table 9.

Table 10.

Table 11.

Table 12.

Table 13.

Table 14.

Table 15.

Table 16.

Elemental Analysis

Infrared Spectra

Ultraviolet Spectra

Crystallographic Data

Schemes of Refinement

Final Atomic Parameters ofNonhydrogen Atoms forC£Co{H2dmg) (dmg) (clan)

Final Parameters for theHydrogen Atoms forC£Co(n2dmg) (dmg) (clan)

Final Atomic Parameters forthe Nonhydrogen Attorns ofC'tCo(H2dpg2) (clan)

Final Parameters forHydrogen Atoms forC£Co(H2dpg2) (clan)

Final Atomic Parameters forNonhydrogen Atoms of[Co(Hdmg) 2 (clan) 2]C-e

Final Pararaeters forHydrogen Atoms for[Co(Hdmg) 2 (clan) 2]C£

Selected Interatomic Distancesin Some Cobaloxime Complexes

Selected Interatomic Anglesin Some Cobaloxime Complexes

Deviations andSelected Lcast-in C£Co(H2dmg)

(

Deviations andSelected Least-in C£Co(H2dpg2)

Deviations andSelected Least-in [Co (Hdmg) ~ (c

Equations ofSquares Planesdmg) (clan)

Equations ofSquares Planes(clan)

Equations ofSquares PlanesIan) 2]C£

8

10

15

18

28

33

35

37

41

43

45

52

54

59

61

63

vx

Table 17.

Table 18.

Hydrogen Bonds in Cobaloximes

Dihedral Angles Formed by

Selected Planes in SomeCobaloxime Complexes

Table 19. A Summary of the Average Bond

Distances in XYCo(H2dmg2)Complexes

Bond Distances and Bond Angles

of Coordinated 4-ChloroanilineMolecules

Bond Distances, Bond Angles, and

Least-Squares Planes of Phenyl

Rings in C£Co (H2dpg2) (clan)

Final Atomic Parameters of

Nonhydrogen Atoms forH2dhphpy(N03)2'^H20

Final Parameters for the

Hydrogen Atoms inH2dhphpy(N03)2-2H20

Final Atomic Parameters of

Nonhydrogen Atoms for

[Ni2C£ {H2O) 4 (dhphpy)

I

Cl^ • 2H2O

Final Parameters for the

Hydrogen Atoms in

[HiyCl (H2O) 4 (dhphpy)

]

Cl^

'

2H2O

Selected Interatomic Distances

for H2dhphpy(N03) 2-2H20 and

[Ni2C£ {H2O) 4 (dhphpy)

]

Cl^

'

2H2O

Selected Angles inH2dhphpy(N02)2'2H20

Table 20.

Table 21.

Table 22.

Table 23.

Table 24.

Table 25.

Table 26.

Table 27.

Table 28.

Table 29.

Table 30.

2H2OSelected Angles in

[Ni2C£ (H2O) 4 (dhphpy)

]

Cl^

Hydrogen Bonds inHodhphpy(N03) 2-2H20 and[Ni2C£ (H2O) ^ (dhphpy)

]

Cl^

•

2H2O

Deviations and Equations of

Selected Least-Squares Planes

in H2dhphpy (N03)2-2H20 and

[Ui^Cl (HO) 4 (dhphpy)

]

Cl^ • 2H2O

64

73

77

80

81

85

86

88

92

98

100

101

103

109

Vll

Table 31

Table 32.

Table 33

Table 34

Table 35.

Table 36

Table 37

Table 38

Table B-1.

Table B-3

Table B-4

Table B-5,

Final Atomic Parameters for theNonhydrogen Atoms inC4 (fph) 4C0 (cp) (tpp) andC4(fph)4Rh(cp) (tpp)

Selected Bond Distances ofC^(fph)^M(cp) (tpp)

Selected Bond Angles ofC^(fph)^M(cp) (tpp)

Deviation from and Equationsof Some Least-Squares Planesof C4 (fph) 4Co(cp) (tpp) andC4(fph)^Rh(cp) (tpp)

Average C-F and C-C Distancesfor the PentafluorophenylGroups in C^ (fph) ^M (cp) (tpp)

Bond Distances and Bond Anglesof Pentaf luorophei^iyl Groupsin C^(fph)^Co(cp) (tpp)

Bond Distances and Bond Anglesof Pentaf luorop};.enyl Groupsin C^ {fph)^Rh(cp) (tpp)

Bond Distances and Bond Anglesof Triphenylphosphine inC^(fph)^M(cp) (tpp)

Observed and Calculated StructureFactors for C£Co (H^dpg^) (clan)

119

Table B-2. Observed and Calculated StructureFactors for [Co(Hdrag) (clan) ]C£

Observed and Calculated StructureFactors for H-dhphpy (NO^) „

• 2H

Observed and Calculated StructureFactors for [Ni„C£ (H^O) . (dhphpy) ]

-

C£2*2H20 ^

Observed and Calculated StructureFactors for C , (fph) .Rh (cp) (tpp)

128

129

130

133

134

136

138

156

173

181

190

205

vixi

LIST OF FIGURES

Figure 1. An ORTEP drawing of 47

C£Co(H2dmg) (dmg) (clan) •2H2O

Figure 2. An ORTEP drawing of 49

C£Co(H2dpg2) (clan) •C2H3OH

r: 51Figure 3. " An ORTEP drawing of

[Co (Hdmg) 2 (clan) 2KC

Figure 4. A projected view along Co-N(l) 70

for CCCo(H2dmg) (dmg) (clan)

Figure 5. A projected view along Co-N(l) 72

for (a) [Co(ndrag)2(clan) 2]C£

and (b) CCCo (H2dpg2) (clan)

Figure 6. An ORTEP drawing ofH2dhphpy (N03)2'H20

Figure 7. An ORTEP drawing of[Ni2C^ (}l20) 4 (dhphpy) ]C£3- 2H2O

A packing diagram of 1^^

H2dhphpy (NO3) 2-2K20Figure 8,

Figure 9. A packing diagram of[Ni2C£ (II2O) 4 (dhphpy) ] 0^3 • 2H2O

Figure 10. An ORTEP drawing ofC4(fph)4Co(cp) (tpp)

95

97

108

126

IX

KEY TO ABBREVIATIONS

LIPS ligand-induced proton shift

H-dmg dimethylglyoxime

dmg dimethylglyoxime dianion

Hdmg ' dimethylglyoxime monoanion

Hpdmg- bis (dimethylglyoximate) withrelative proton positionsunspecified

sulfa sulfanilamide

dhph 1, 4-dihydrazinophthalazine

dhphpy 1, 4-dihydrazinophthalazinebis (2-

pyridinecarboxaldimine)

pyca 2-pyridinecarboxaldehyde

clan 4-chloroaniline

Hjdph diphenylglyoxime

Hjmpg methylphenylglyoxime

fph pentaf luorophenyl

cp cyclopentadienyl anion

tpp triphenylphosphine

an aniline

4-FPYTSC 4-formylpyridinethiosemicarbazone

Abstract of Dissertation Presented to the Graduate Councilof the University of Florida in Partial Fulfillment of the

Requirements for the Degree of Doctor of Philosophy

X-RAY STRUCTURAL STUDIES OF SOME GROUP VIIICOMPOUNDS WITH CATALYTIC IMPLICATIONS

By

Douglas Allen Sullivan

December, 19 75

Chairman: Gus J. PalenikMajor Department: Chemistry

X-ray structural investigations of compounds containing

Group VIII metal atoms are presented. The compounds studied

illustrate interatomic interactions which may be of impor-

tance in catalytic processes. The structures of metal-con-

taining compounds were solved by locating the heav;^' atoms

in Patterson functions and locating the remaining atoms in

Fourier syntheses. The direct method of symbolic addition

was used in the one, all light-atom case presented. Trial

structures were refined by the method of least-squares.

The crystal structure of trans-chloro (dimethylglyoxima-

to) (dimethylglyoxime) (4-chloroaniline) cobalt (III) illustrates

an unusual ligand-induced proton shift. Both neutral and

dianionic dimethylglyoxime groups are found in the complex

and the 4-chloroaniline ligand is oriented over the dianion-

ic dimethylglyoxime. The structure of trans-bis (dimethyl-

xi

glyoximato) bis (4-chloroaniline) cobalt (III) chloride shows

that complex to contain two monoatomic dimethylglyoxime

ligands and the 4-chloroaniline ligands to be skewed rela-

tive to the diglyoxime ligands. The crystal structure of

trans-chlorobis (diphenylglyoximato) {4-chloroaniline) cobalt-

(III) is described. Trends in the structures of these com-

pounds and in the previously reported structures of similar

compounds are discussed. Ultraviolet and infrared spectra

of these compounds are given.

The synthesis of a novel chelating ligand capable of

binding two metal ions is described. The characterizations,

including crystal structures, of its protonated forin, 1,4-

dihydrazinophthalazinebis (2-pyridiniuracarboxaldimine) nitrate

dihydrate, and of a nickel complex, y-chlorotetraaqua []. ,4-

dihydrazinophthalazinebis (2-pyridinecarboxaldimine) ]dinickel-

(II) chloride dihydrate, are presented. The planar ligand

is shown to bind tv/o nickel ions with a separation of 3. COSo

(1) A. A chloride ion occupies a bridging site in the plane

of the nickel atoms and the ligand. The magnetic moment per

nickel atom of the chloride bridged complex was deteinnined

to be 2.74 B.M. at 40°C. The plausibility of structurally

similar complexes mimicking the nitrogen-fixing enzyme

nitrogenase is also discussed.

The X-ray crystal structures of 1- (ir-cyclopentadienyl)

-

l-triphenylphosphine-2 ,3,4, 5-tetrakis (pentaf luorophenyl) co-

baltole and 1- (Tr-cyclopentadienyl) -1-triphenylphosphine-

2 ,3, 4 , 5-tetrakis (pentafluorophenyl) rhodole are reported.

xii

These compounds are viewed as stabilized intermediates in

the catalyzed cyclization of acetylenes. In each case the

metal atom forms a metallocyclo by a-bonding to the ter-

minal carbons of a butadiene-like fragment. The ir-bonding

in the metallocycle appears to be dclocalized.

XI 11

CHAPTER 1

INTRODUCTION

Western civilization has demonstrated the efficiency-

oriented phenomenon of expending large amounts of energy to

find ways of requiring less human energy. This is evident in

the evolution from animal trails to freeways and from muscle

to sophisticated, high-energy machinery. On the molecular

scale the more efficient path io provided by catalysts. As

alchemists searched for the "philosopher's stone" many chemists

have been seeking catalysts. The application of catalysis is

now advancing through the development of an understanding of

the mechanisms of catalytic processes.

Life processes are dependent upon chemical reactions

controlled by enzymes. "It is not generally appreciated how

little is understood about the mechanisms by which enzymes

bring about their extraordinary and specific rate accelera-

tion." Investigation of enzymes should not only be fun-

damental in the understanding and maintenance of life pro-

cesses but also should contribute to developing more effi-

cient industrial processes.

Much of the investigation of enzymes has concerned the

use of model compounds. "Model building and the application

of material analogues are becoming increasingly important

for the elucidation of fundamental problems of biochemical

structure and reactivity."^ X-ray structural studies of

enzyme models are important for the exploration of structure-

activity relationships. Solid state studies of enzym- model

compounds are of particular relevance I ocauso of the high

degree of order the macromolecular enzymes themselves possess.

While electrostatic and hydrogen-bonding forces are

usually considered the major binding forces in enzyme-sub-

strate interactions, the strong charge-solvating and hydro-

gen-bonding ability of water tends to reduce the possibility

of obtaining large binding energies from these forces. To

explain the large binding energies found, "hydrophobic forces"

are presumed to exiso in these intermolecular interacions in

aqueous solution.^ The enthalpies of mixing of aromatic li-

quids with aliphatic liquids indicate that aromatic mole-

cules prefer an aromatic environment. ' "Stacking interac-

tions" involving the 7i-systems of aromatic groups within the

enzyme's protein structure may account for part of the "hydro-

phobic forces" and contribute to the orientation of the enzyme-

substrate interaction.^ The ligand-induced proton shift (LIPS)

observed in ClCoiU^dx^g) (dmg) (sulfa) [the key to abbreviations

is given on page xl is an indication of the importance of this

TT-type interaction. A further examination of LIPS v. as under-

taken and is presented in this work.

The design of enzyme models is often based on sparse

structural information about the prosthetic group of the en-

zyme. Efforts to miiTLic the nitrocen-f ixing enzyme nitrogenase

have been concerned with the metal to nitrogen bond. The

6 7probable binuclear nature of the enzyme's active site ' has

largely been ignored. The structures of a novel binuclea-

ting ligand and its nickel (II) complex are presented here

as a first step in the construction of a new generation of

models for nitrogenase.

When the mechanism of a chemical process is believed

to be understood, stable compounds similar to the interme-

diates of the reaction may be prepared and examined to

support the proposed mechanism. One proposed mechanism for

the catalyzed cyclization of acetylenes v/ould have a five-

membered ring containing a metal atom and a cyclobutadiene

8— 1 3fragment as one of the intermediates. The first struc-

ture of such a stabiliF.ed intermediate containing a cobalt

atom and the structure of the rhodiv;m analog are presented

in this study.

CHAPTER 2

SYNTHESIS AND CHARACTERIZATION

Synthes is

Crystals of all cobaloxime compounds were generously

provided by R. C. Palenik* and were used v.'ithout recrys-

tallization.

M. D. Rausch and R. H. Gastinger synthesized the

14 15metallocycles containgmg cobalt and rhodium. They

supplied well-formed crystals of those metallocycles for

X-ray structural studies.

Unless otherwise indicated all solvents were reagent

grade and were used without further purification. All pre-

parations were carried out in air. All melting points were

taken on a Mel-temp apparatus in open capillaries and are

uncorrected.

16The published method was used to prepare dhph for

succeeding experiments. To 6.40g (49.0 mmoles) 1,2-dicyano-

benzene (98%; Aldrich Chemical Corripany, Milwaukee, Wise.) in

12.5 ml 1,4-dioxane was added a mixture of 15.0 ml (ca. 250

mmoles) hydrazine hydrate (85%; Fisher Scientific Company,

Fair Lawn, N. Y.) and 4 . ml glacial acetic acid (reagent;

Baker and Adamson, Morristown, N. J.). After being heated

*These complexes were prepared using standard procedureswith synthetic details to be published at a later date.

for three hours the mixture was cooled and the red product

was collected (yield, ca . 40%). The decomposition temper-

ature of 193 °C was in agreement with the reported value.

A solution of 0.0955g (0.50 mmoles) of the previously

prepared dhph in 4 ml absolute ethanol was added to a solu-

tion of 0.237g (1.0 mmoles) UiCl2' ^^2^ (reagent; Matheson,

Coleman and Bell, Norwood, Ohio) and 0.095 ml (0.99 mmoles)

pyca (99%; Aldrich) in 40 ml absolute ethanol. Upon slow,

almost complete, evaporation in air of that solution olive

green crystals of [Ni2C£. (H2O) ^ (dhphpy) ] 0^3 • 2H2O formed.

Analogous procedures were carried out replacing NiC£2

*

H2O with CoCl2'^^-2^' CuC£2 '2^120 (reagent; Fisher), ZnCl2

(reagent; Mallinckrodt Chemical Works, St. Louis, Mo.) and

FeC£2'4^2^ (reagent; r4atheson, Coleman and Bell) without

success in obtaining a crystalline product. Similar pro-

cedures were followed with the addition of ca. 0.2 ml of

12 M hydrochloric acid (reagent, 38%; Baker and Adamson) to

solutions of CuC£2'2H20 and FeCc2'4H20. Again, no suitable

products were formed. Attempts to separate and recrystallize

reaction products from water, water-ethanol , methanol and

pyridine failed to give a crystalline product. V7hen CuC£2

was present, gas evolved from the reaction mixture.

Additional attempts wore made to isolate complexes

similar to {Ni C(l (H 0) (dhphpy) ] Ci^ using dhph obtained by

recrystallization from hot water of H2dhphS0^ (ICN-K and K

Laboratories, Ir>.c. , Plainviev/, N. Y.) to which an equivalent

amount of KOH (certified A.C.S.; Fisher) had been added.

Those attempts were unsuccessful.

The red-orange plates of H2dhphpy (NO^) 2^ 2H2O used in

crystallographic studies had been recrystallized from water.

The crude product formed upon cooling a solution made by

adding 0.190g (1.0 mmole) dhph in 20 ml warm water to a

solution containing 0.583g (2.0 mmoles) Ni (NO-^) 2 ' ^H^O (re-

agent; Mallinckrodt) and 0.8 9 ml (9.4 mmoles) pyca in 10 ml

warm water followed by drop-wise addition of nitric acid

(reagent, 71%; Baker and Adamson) to a pH less than 1.

Also, H^dhphpy (NO^) 2 was prepared by first adding 1.90

ml (20.0 miaoles) pyca to a suspension of 2.878g (10.0 mmoles)

H2dhphS0. in 100 ml water. A brick-red solid formed upon

addition of l.llg (ca. 17 mmoles) KOH. After washing with

water and drying in air, the brick-red solid was suspended

in 100 ml of 95% ethanol and 1.30 ml (21 mmoles) of nitric

acid were added. Small red-orange needles of H2dhphpy (NO^)

2

which decompose at 126°C were filtered, v;ashed with ethanol,

and then ether and air dried (yield 4.0g, 75%).

Freshly prepared hydrated metal hydroxides were reacted

with H2dhphpy (NO^) 2 in methanol. Each of the metal hydroxides

was filtered after adding 1 M KOH to aqueous solutions of

Ni(N02)2-6H20, Cu (NO^) 2' 3H2O (reagent; J. T. Baker Chemical

Company, Phillipsburg, N. J.), Fe (C^O^) 2• 6H2O (reagent; G.

Frederick Smith Chemical Company, Columbus, Ohio) and

Zn(NO,)2-6H (reagent; Matheson, Coleman and Bell). After

the reaction mixtures were stirred until there was no further

change in color, they were filtered and the filtrates were

allowed to evaporate. Only the reaction with nickel (II)

hydroxide produced a crystalline product. Attempts to re-

crystallize that maroon product from methanol, ethanol,

ethanol-water, and 2-propanol did not yield crystals suitable

for crystallographic studies.

Discussion of Characterization

The microananlyses recorded in Table 1 were performed

by Galbraith Laboratories, Inc., Knoxville, Tennessee, for

the dhphpy compounds and by Atlantic Microlab, Inc., Atlanta,

Georgia, for the cobaloxime complexes. The calculated per-

centages of carbon, hydrogen, and nitrogen for the dhphpy

compounds correlate well with the measured percentage. Two

water molecules per molecule of dhphpy in each are indicated

by the elemental analysis. This is confirmed in the struc-

tural determination. Similarly, the eleraental analysis of

C-tCoCH^dmg) (4-nitroaniline) is in agreement with the expected

formula with tv;o water molecules present. Based on the

measured density and crystallographic data the molecular

weight of [Co (H2dmg2) (4-methylaniline) ] c£ should be 596.

This is greater than its formula weight of 538.9 and the

presence of molecules of solvation is expected. Three water

molecules or one molecule of the ethanol solvent per formula

could account for the difference. Neither of these possi-

2Of

U

(0

o

13c

O

UrH(0

o

in

bilities is confirmed by the CHN analysis (see Table 1)

.

IR spectra of samples as mineral oil mulls between

polished plates of fused sodium chloride were recorded on a

Beckraan Model IRIO grating spectrophotometer from 4000 to

500 cm" . The spectra were calibrated using the 1601.0 cm

absorption of a polystyrene film. IR spectra of selected

compounds are reported in Table 2. The IR spectra of the

bis (diglyoxime) cobalt (III) complexes with aniline derivatives

exhibit many features of similar cobalt complexes with nit-

, 18riles and isonitriles described by Batyr et al . The

18spectra of the cobaloximes shov; the absorption assigned to

the C=N stretch between 15 50 cm" and 158 cm . The ab-

18 -1sorptions associated with the N-0 band at ca. 124 5 cm

and ca. 1095 cm" are present also. A weak absorption in

the 1700-1800 cm" range appears in some of the spectra but

with lov/ resolution. Peaks in this region have been

assigned to the 0---H-0 bridge between the dioximate

ligands. The presence of a symmetrical bridge has been

20suggested to rationalize this low frequency.

Absorption spectra in the ultraviolet region were re-

corded on a Gary Model 15 spectrophotometer. Spectra of

solutions were measured from 26.7 kK (375 my) to 47.6 kK

(210 my) using the double beam method with the pure solvent

as the reference. Solutions of the cobaloxime complexes in

methanol (spectroquality ; Matheson, Coleman and Bell) and

solutions of the diiphpy compounds in 0.1 M hydrochloric

10

CM

0)

EH

(0

3O

tu

Q)

-PO0)

iH<D

CO

o

+J

O(1)

a,

730)

V4

03

U

c

I

ae

^ cO (fl

I

(N

-OfNK —^ CO fO

^N* U

0)

c1 -H

CN-HCn CB 03

'9 O(N uE -P

o du I

u ---

I ^^ 03

-d :3

(N U5

O CT"

U E

I

(NO

O ^^u e=^1 73u ^

i S S 3o o m in00 vri vD vo^ n i-H on n ro ro

U) (0 V)

00

in

11

C•HPcoo

CM

0)rH

(0

CM

E

-- cO (C

U rH«s> Uu —

CM

12

0)

0)

0)

OJ

Eh

oI EG, •

j:: CM

TJ OrM52

I

o uCM,—

.

^ >i"^^ a,u x:fN ou•H x:Z T3

e^

13

0)

c•H+)

O

•0

X0)

C4

0)

Id

oCM

I Ka •

'O O

I

O UCNr-.

K --

''^ au 4::

cNa•H x;

u

14

acid were used. The UV spectra are reported in Table 3.

The UV spectra of all these compounds are dominated by

21intense charge transfer bands. Yamano et al . report thrde

bands in this region for compounds of the formula [Co(H2dmg2)-

A ] where A is an aniline derivative. These three bands are

present in [Co (Hdmg) 2 (clan) 2] C-t and [Co (H2dmg2) (4-methyl-

aniline)2]C£. The band between 25.0 and 27.5 kK (400 to 360

my) was assigned^-*- to the charge transfer from the aniline

ligand to the cobalt ion. In agreem.ent with this assignment

the band for the complex of the more basic 4-methylanJ line

at 27.6 kK is lower in frequency than that for the analogous

complex of clan at 28.9 kK. The band near 33.0 kK (300 my)

was assigned^ "" to the charge transfer from the cobalt ion to

the dioximate ligand. The band near 40.0 kK (250 my) was

assigned'*'"'" to the intra-Hdmg tt-^-it* transition.

The UV spectra of cobaloxime complexes with a cliloride

ligand tran s to a substituted aniline shov/ three bands, also.

One band is between 27.0 and 33.0 kK (370 to 300 my). The

other bands lie near 39.0 kK (255 my) and 43.0 kK (230 my).

No assignments have been made for these three bands.

The charge transfer spectrum of a solution of [Ni2Ct-

(H-0) . (dhphpy)]C£-. •2H in 0.1 M HCl exhibits the same ab-

sorptions as that of a solution of H2dhphpy (N02)2 ^^ 0-^ ^

HCl. The intense bands at 25.4, 32.7, and 37.3 kK (395, 305,

and 268 my) are presumably due to the aromatic system of the

ligand.

15

o

16

The magnetic moment per nickel atom of (Ni„C-£ (H^O)

-

{dhphpy)]Cf was determined to bo 2.74 D.M. at 40''C. Data

22 23for this calculation ' were obtained using a Varian A-60A

Analytical NMR Spectrometer and aqueous solutions containing

2% by volume t-butanol as the indicator. This magnetic

moment is in agreement with those of binuclear complexes of

24nickel reported by Ball and Blake. Their complexes of the

general formula [Ni (dhph) ] _X . 'nll^O (X = Cl, Br, or I) had

room temperature effective magnetic moments ranging from

2.79 to 2.89 B.M. As in the case of [Ni (dhph)]

2X . •nH20,

2+where two Ni ions are bridged by a conjugated system,

spin-spin interaction is indicated in [Ni„C^ (H^O) - (dhphpy) ]

-

CHAPTER 3

X-RAY DIFFRACTION EXPERIMENTAL

Except where noted in the text, the experimental methods

described in this section were used in preliminary crystallo-

graphic examination, collection and processing of data, and

refinement of trial structures.

Data obtained using precession and Weissenberg X-ray

25-27photographic techniques were used m determining the

preliminary space groups and cell constants. After centering

fifteen intense reflections d.a computer-controlled Syntex

pT dif fractometer and selecting an indexing consistent with

preliminary photographs, accurate call constants with esti-

mated standaxd deviations vere obtained from least-squares

fittings of 2G, J?,x / and f or those reflections. In each

case the orientation matrix for data collection and the unit

cell volume with its standard deviation were derived from

these data. The calculated density was in agreement with

28the density measured by the flotation method except in the

cases of the metal-containing heterocycles. The specific

gravity of the flotation liquid was measured to ±0.01 with

a precision hydrometer. Relevant crystallographic data for

each of the compounds studied are given in Table 4.

The suitability of a crystal for data collection was

determined by its physical shape and size, the ease v;ith

17

10

O ""S"int, ^ffi ^CM •» (NU O C31

• <N E-- K ^0C CN CMro • KU«N> O— U U—. ,-,c^

tP >ia a *

'd X HfN a.

o ^ c

<N> .-- rHu o o

CQ —- «N

- u ao cN e

m 2; w cj

O f^^ - u --

"=!• rH

oc1-1

(1) HC(0

o o

.-. m4J -uCr>0 ~- QJ

e 2 — efO --' Cli I

^- x; x: -—o aa^ <Nu x: >«< cr>

<^ 'O '- e

K Oi <N

D -^ O

o •- —u o -

CM .»

a;

nr-l JJ Ku

-Hx:Dj <n a—(0 -^ U 0)

U en— Ccr> e o -HO T) U -H

rH — -- a(0 o x: (T3

-P CJ Q, Oen •—-y-i >-i

>i -- -p

u u u c

0) a,

c3 o

(C 0)

e uo c+» cu

in to

m -p

U t/3

f3

1-1

C3OOiEOu

(N

(N

in

o

Ou

U

u o O

CMc

o --

cC .-I o

Oin

fNu

Oin

Z00(N

o;;^

inCN

CN

sD

M-* -^ •^^ ^-^

oCJCN

CJ

CJ

OU

uofN

O(N

u u

oCM

CM

oCN

CO

CN

Uo(Nl

U

o

oCN

oCN

x:in

CN

Dmo

o

oCN

SiouCN

Cn

in in CN

OCN

CN•

O?-.

oCN

ouu

u u u u

o

rH

19

<u

-dG0)4J

0)

<u

(0

0)

E

O o<> ---

>- o

ca

o o<:

XI o<:

(t o <

c

o

eoa

ro

CTl

<N

fO

oCTl

fN

LD

2J

i>D

a\

CO

LD C7> n00

20

0)

xi

0)

X

Eh

21

G0)

Q)

EH

mo

oJ3

tn

CO•H-P

<D U

H mD a:;

«

c

o

3.

o

o

(Q

22

which the reflections wore centered on the diffractometer

,

and the values of the refined cell constants with their

estimated standard deviations compared to the cell constants

obtained by photographic methods. All intensity measure-

ments v;ere made with a fyntex PI diffractometer at ambient

temperature. All unique refelctions up to a limiting 26

value were measured using a variable speed 0-20 scan tech-

nique. The scan rate was determined from a fast throe-

second counting scan of the reflection peak and varied lin-

early from l°/rainute for counting rates of 150.0 c/scc. or

less to 24 "/minute for 1500.0 c/sec. or more. The intensity,

1/ was defined:

T / 4. \ r /i. J. T ^ \ {bac):ground counts) ,I=(scan rate) total scan counts)—,r:

—

-, j j. /—;] .(background to scan rate)

Peaks were scanned from 1'^ below Ka, to 1° above Ka„. Mea-

surements of the background count were made at the limits of

each scan. The estiraatod standard deviation, o(I), of each

reflection was taken to be:

„fT\-r f4.^*.-.-\ ^ J- \ ,(background counts)

i 1/2a(I) = l (total scan counts) + ,r-'T -"j-z r--—r^ J(background to scan ratio) •^

For molybdenum radiation, the incident beam was monochro-

matized by a low order reflection of graphite. Any changes

in the system were detected by measuring four standard re-

flections after each 96 intensity measurements.

A standardized data set was obtained by scaling the

data to the initial value of the sum of the measured in-

tensities of the standard reflections. The scaled in-

23

tensities of duplicate or equivalent reflections were av-

eraged. Reflections with an intensity greater than Ka(I),

where K is given in Table 4, were considered reliable. The

unreliable reflections with I<Ka(I) were identified by a

minus sign and not included in further steps of the struc-

ture solution. Corrections for Lorentz-polarization were

of the forcv:

1 _ sin 26 .

Lp (l+cos^28)

To obtain a set of observed structure factors, ^obs'^'

the monochrciriator wao also assumed to be 50% perfect crystal

and 50% mosaic crystal.

Scattering factors v/ere obtained from Hanson, Herman,

29 3Lea, and Skillman; Stewart, Davidson, and Simpson; Doyle

and Turner; and are uncorrected for anomalous dispersion.

The natural log of the scale factor and the overall temper-

32ature factor were initially estimated from a V7ilson pilot.

The initial choice of a centric or acentric space group was

33made on the basis of calculated intensity statistics.

In the case where molecules contained at least one heavy

atom (Atomic Number -^ 16) the approximate positional co-

^ • 3 4 ^ordinates were determined using a Patterson function of

the form:

P(UW7) =- Z Z E |F(hkl) l^cos27r{hU+kV+lW) .

h=-°° k^-"- l=-<»

Using the location of the heavy atom(s) in a structure

24

factor calculation allowed a sufficient number of reflection

phases, a(hkl)'s, to be assigned. The magnitude of the

structure factor,|

F^^,^ |, and the phase may be defined by

27the following equations:

A^, , = Ef . cos 2TT(hx. + hy. + Iz.)hkl .J 3 D 3

B , , = If. sin 27r(hx. + hy . + Iz )

where f . is the scattering factor for atom j.

Additional atomic positions could then be determined

through the use of Fourier syntheses of the form:

OO 00 CO

(XYZ) =- E Z Z l^hkl'^°^ 2tt[ (hX+kY+lZ)-a^j^^] .

V h = k=-<» l^-o)

The positional coordinates of atoms in the trial structure

were estimated froir. the Fourier generated electron density

map using a FORTRAN computer program, BOOTHITl, written in

the course of this work. A description and listing of

BOOTHITl is contained in Appendix A. Alternate structure

factor calculations and Fourier syntheses were repeated

until all nonhydrogen atoms were located.

In the case of a compound not containing a heavy atom

but having a centrosymmetric space group, the direct method

of symbolic addition was used. The FORTRAN computer programs,

FAKE-MAGIC-LINK-SYMPL, developed by E. B. Fleischer, R. B.

25

K. Dewar, and A.L, Stone ' were used to generate possible

solutions to the phase problem. The programs first converted

If , I's to normalized structure factors, E's, through the' obs '

definitions:

fp )2 ^ J^I

,2 (T sin G)/X^ absolute^ ^2 'obs'

and

2 2^2absolute . i

where the scale factor, K, and the overall temperature fac-

tor, T, were generated by a Wilson plot; where e was a

symmetry factor applied to reflections in special zones; and

where f.'s were the scattering factors for N atoms. The pro-

grams then assigned symbols representing the phases to six

of the largest E's having the greatest number of interactions,

i.e., for E^ aiid E there exists E, . For such reflections' h n. h-m

the probability, p, the.t the phase of E, is the same asNE (E E, ) is given by:

m h-m ^ -^

m=0

p = 0.5 + 0.5 tanh (-^-lE^i! ^ ^ E^-n,!)a » 1 . 5 m=^

whereN

^ j=l 3

with N being the number of atoms in the unit cell and Z. being

the atomic number of the j atom. The programs, when given

minimum acceptable probability criteria, iteratively assigned

relative signs to the phase symbols. Combinations of these

26

signed phase symbols were finally used in conjunction with

their structure factors to generate E-maps. The positional

coordinates of most nonhydrogen atoms were determined from

one of these E-maps. Structure factor calculations and

Fourier syntheses were used to refine the atomic positions

and, as in the heavy atom case, to locate any previously un-

found nonhydrogen atoms of the trial structure.

The trial structure was refined by least-squares

34minimization of the function:

Residual =2w(l|F^^^| - If^^^^ID^

where

.ow

and

' obs '' low' ' obs '

' 1<

' low' — ' obs' — ' high'

^^^ I^high!/l^obsl ^°^ l^obsl > l^high!

F, and F . , are constants given in Table 4. Prior to re-low high

finement, an overall scale factor was chosen such that the

sum of F ^ equaled the sum of F , . Isotropic temperatureobs ^ calc

factors were used in the first three cycles of refinement

and then anisotropic temperature factors of the form:

exp[-(3j^^h^ + 622^^ ^ ^^33^^ '^ ^12^^ "^ ^13^^^ "^ B23h£)]

were used. The reliability index, R, was defined by:

K —

' obs

27

Calculations were performed on an IBM 370/165 computer

with programs written or modified by Dr. Gus J. Palenik,

except where previously noted. The refinement of each

structure is outlined in Table 5.

28

x:

29

en

U4

o

fo

CHAPTER 4

AN INVESTIGATION OF LIGAND-INDUCED PROTON SHIFT: THE CRYSTALAND MOLECULAR STRUCTURES OF TRANS-CHLORO (DIMETHYLGI.YOXIMATO)

-

(DIMETHYLGLYOXIME) (4-CHLOROANILINE) COBALT ( III ) DIHYDRATE,TRANS-CHLOROBIS (DIPHENYLGLYOXIMATO) ( 4-CnLOR07U\:iLINE) COBALT (HI)ETHANOLATE, AND TRA_NS~BIS (DIMETHYLGLYOXIMATO) BIS (4-CHLO.HOANI-

LINE) COBALT (III) CHLORIDE.

The stability of bis (dimethylglyoxiine) metal coiriplexes

has long been known and their importance in both qualitative

37 3 8and quantitative analysis has been widely recognized. '

Metal complexes of Hdmg have been used to study tlie trans -

39 40 41effect and the trans -influence ' of various ligands in

octahedral complexes. Since the structural determination of

the B, „ coenzynie the trans -bis (dimethylglyoxime) cobalt com-

42-44 42plexes have become of considerable interest. Schrauzer

has stated that to be capable of mimickiug P^ ^ ^ complex is

required only to have a cobalt ion in tiie presence of a strong-

binding planar ligand. Because Co(H„dmgp) complexes success-

fully mimic the reactions of a cobalt ion in the corrin ring

and because they are synthetically expedient, complexes of

Co(H»dmgp) have been investigated extensively in solution as

45models for B, „

.

Until very recently there have been few structural data

on Co(Hpdmgp) complexes. ' ' Except for the work of

46Palenik et al . no structural investigation has been made of

the interaction between the axial ligand and the equatorial

Hdmg ligands. This interaction may be of considerable con-

sequence.

30

31

Although sulfonamides are potent inhibitors of carbonic

anhydrase they do not form strong coordination bonds with

transition metal ions. Therefore, an interaction of the aro-

matic ring of the sulfonamide with the carbonic anhydrase pro-

53tein has been proposed to make a large contribution to the

observed stability of the carbonic anhydrase-sulfonamide com-

plex. Since a cobalt atom can replace the zinc atom in car-

bonic anhydrase with only a 50% decrease in activity, complexes

of Co(H_dmg2) '^^Y pri.^ve to be useful models for investigating

the interaction of sulfonamides with carbonic anhydrase.

An apparent ligand-- induced proton shift (LIPS) was ob-

served in C-^Co (H2dmg2) (si.ilfa) which should be formulated

C-^Co (Kpdmg) <dmg) (sulfa) . To investigate further the LIPS

phenomena and to examine inter ligand interactions within this

type of complex the determination of the structures of C.£Co-

(H2dmg) (dmg) (clan) , [Co (Hdrag) 2 (clan) 2] C£, and C£Co (H2dmg2)

~

(clan) was undertaken.

Structure Solution and Re finem.ontfor C£Co(H2dmg) (dmg) (clan) '2lIoO

The heavy atom method was used with the positions of the

cobalt atom and of the ionic chloride ligand estimated from

a sharpened Patterson function. The magnitude of the Patter-

son function for the Co to C£ vectors was of the same order

as that for the Co to Co vector. The positions of the heavy

atoms, therefore, appeared ambiguous and several combinations

were used in Fourier syntheses to determine their actual lo-

32

cations, successive Fourier syntheses then revealed the loca-

tions of all nonhydrogen atoms in the compound. Three cycles

of full-matrix least-squares refinement with individual iso-

tropic thermal parameters and then three cycles of least-

squares refinement using. the block approximation with indi-

vidual anisotropic thermal parameters reduced R to 0.066. A

difference Fourier synthesis then indicated the absence of

additional nonhydrogen atoms and revealed the positions of

all hydrogen atoms. An outline of the refinement is given in

Table 5. The refinement was terminated after the parameter

shifts for the nonhydrogen atoms were less than one-tenth of

their corresponding estimated standard deviations.

The scattering factors for cobalt, chlorine, oxygen,

nitrogen, and carbon were from Hanson et al.^^ while those

for hydrogen were from StewarL e.L_al.-° A list of the observed

and calculated structure factors has been published and is

available.'''^ The final positional and thermal parameters are

given in Tables 6 and 7.

Structure Solution and Refinement

for C^Codl^dpg-;,) (clan) -C^H^OH

The nonstandard space group P2j^/n was chosen since the

standard P23,/c space group would require a very large value

for B. The position of the cobalt atom was estimated from a

sharpened Patterson function. The location of atoms and the

refinement proceeded as in the case of c£Co {Il2dmg) (dmg) (clan) •

2H2O. Two atoms, 0(S1) and C(Si), of an apparent solvent mole-

33

Table 6

Final Atomic Parameters of Nonhydrogen Atoms for c£Co(H2dmg)-

(drag) (clan)^

Atom

34

Table 6 - extended

^33 ^12 ^13 ^23

276(4) 822(17) 219(13) 157(9)

53(1) 78(4) 25(3) 14(2)

138(2) 65(7) 46(7) 46(4)

36(3) 168(14) 7(9) 44(6)

32(3) 167(13) 70(9) 33(6)

41(3) 199(14) 74(10) 70(6)

30(3) 199(14) 31(9) ,25(6)

37(3) 123(14) 29(10) 50(7)

35(3) 108(14) 24(10) 26(7)

35(3) 71(13) 30(9) 19(6)

41(3) 123(14) 41(10) 39(7)

35(3) 99(13) 21(10) 12(7)

53(4) 101(17) 25(13) 41(9)

51(4) 73(16) 30(13) 14(8)

76(5) 190(21) -5(16) 55(10)

62(5) 214(22) 50(16) -6(10)

56(4) 134(18) 47(14) 44(9)

60(5) 110(17) 52(13) 24(9)

102(7) 347(31) 148(24) 106(14)

73(6) 301(28) 37(20) 11(12)

44(4) 72(15) 23(11) 44(8)

47(4) 89(17) 4(13) 28(9)

42(4) 95(19) 4(14) 8(9)

82(6) 61(18) 23(16) 39(10)

69(5) 99(20) 83(16) 95(11)

52(4) 104(18) 56(13) 52(9)

80(4) 241(16) 102(11) 100(8)

53(3) 295(16) 20(10) 22(7)

35

Table 7

Final Parameters for the-

(clan)^

36

cu]c were located before refinement. The scheme of the refine-

ment is outlined in Table 5.

Although the compound was crystallized from ethanol,

difference I'ourier syntheses at various stages of refinement

failed to indicate the position of an additional atom in the

solvent molecule. Because a large region of relative high

electron density existing near C(fl) could be indicative of

an atom with high disorder and because ethanol v/as the sol-

vent, a molecule of ethanol was assumed to be present for the

purposes of determining the formula, molecular weight, and

density

.

The cobalt, chlorine, oxygen, nitrogen, and carbon

29scattering factors wore taken from Hanson e t a

1

. and those

for hydrogen from Stewart et al . Table B-1 is a list of

observed and calculated structure factors for C£Co (H2dpg2)~

(clan) . The final positional and thermal parameters are shov/n

in Tables 8 and 9.

Structure So

l

ution and Refinementfor "ICo (Hdmg) 2 (clan) 2] C?.

With one molecule per unit cell in the centric PI space

group the cobalt atom and the chloride anion were required

to lie on centers of symmetry. The sharpened Patterson func-

tion was ill agreement with tlie chloride ion at 0--iO when the

cobalt atom is placed at 000. The remaining atoms were loca-

ted in a similar manner as in CgCo (H2dmg) (dmg) (clan) . An out-

line of the refinement is given in Table 5.

37

Table 8

The Final Atomic Parameters for the Nonhydrogen Atoms of ClCo

(H2dpg)2

38

Table 8 - extended

B33 '12 6 13 323

19(0)

40(1)

100(3)

21(3)

16(3)

20(3)

21(3)

34(4)

13(3)

26(4)

20(3)

16(3)

23(4)

18(4)

23(4)

28(5)

23(4)

15(4)

17(4)

28(5)

30(5)

36(6)

45(6)

46(6)

37(6)

33(5)

39(5)

29(5)

45(6)

43(6)

32(5)

-7(3)

8(5)

71(9)

12(11

-17(16

-35(13

-18(13

-9 (13

23(11

7 (15

15(1^

-12(14

5(16

-5(18

20 (17

11(17

4 (15

24 (15

43(17

26(16

-5(18

17 (19

45(18

58(19

19(23

69(17

5(17

10(21

12(19

28(2?.

7(22

2(1)

11(3)

96(5)

6(6)

-8(6)

3(6)

-4(5)

7(8)

-6(6)

-1(8)

6(7)

13(6)

16(9)

7(9)

20(9)

-8(10)

12(9)

-4(8)

3(3)

-] (10)

•18(10)

-7(11)

4(12)

40(12)

44(12)

9(10)

31(10)

22(11)

9(11)

30(11)

11(11)

-4(2)

-13(4)

-15(7)

26(8)

7(13)

8(9)

12(10)

-15(12)

14(8)

7(12)

-21(11)

6(11)

20 (13)

0(13)

23(14)

5(13)

-2(12)

7(11)

-9(12)

30(12)

20(14)

15(15)

2(15)

20(15)

70(17)

•29(14)

4(15)

2(16)

46(16)

13 (19)

2(17)

39

Table 8 - continued

Atom X y z ^^^ ^22

C(1B) 6675(9) 2815(14) 3687(7) 61(9) 113(16)

C(2B) 7444(9) 2801(13) 4142(7) 59(9) 89(15)

C(3B) 7498(9) 3363(15) 4781(7) 56(10) 189(23)

C(4B) 6828(9) 4051(16) 4937(7) 59(10) 207(22)

C(5B) 6047(10) 4094(14) 4476(7) 73(11) 148(19)

C(1C) 664(9) 1226(12) 3750(7) 66(10) 73(14)

C(2C) 20(9) 872(12) 4199(7) 56(10) 96(16)

C(3C) -212(9) 1576(14) 4700(8) 32(8) 183(23)

C(4C) 184(9) 2563(12) 4813(7) 61(10) 112(17)

C(5C) 826(8) 2872(11) 4368(6) 60(8) 41(11)

C(1D) 593(9) 2121(12) 1437(6) 54(8) 83(14)

C(2D) -224(9) 1992(14) 1045(7) 56(9) 116(16)

C(3D) -951(9) 2410(12) 1345(7) 50(9) 105(17)

C(4D) -888(8) 2847(12) 2044(7) 42(8) 77(14)

C(5D) -69(8) 2975(12) 2447(6) 30(7) 63(12)

0(S1) 1418(9) 4904(10) 944(5) 190(13) 136(13)

C(S1) 1450(26) 4854(22) 182(12) 512(49) 196(30)

a 4 . .

All values are x 10 . The estimated standard deviationsare given in parentheses. The temperature factors are of

the form: exp[-(B^^h2 + 622^^^ "^ ^33^^ "^ ^12^^^ "^ ^13^^^ "^

3^ok-c) J .

40

41

Table 9

Final Parameters for Hydrogen Atoms for C£Co (Il^dpg„ ) (clan)

Atom[Bonded to] Distance x y z B

H(B1)

42

The scattering factors for cobalt, oxygon, nitrogen, and

29carbon were from Hanson et al . , those for hydrogen wore

from Stewart et al . , and those for chlorine were from Doyle

and Turner. The observed and calculated structure factors

are given in Table B-2. Lists of final positional and thermal

parameters may be found in Tables 10 and 11.

Results and Discussion

The atomic numbering and thermal ellipsoids of C£Co-

{H2dmg) (dmg) (clan) , c£Co (H2dpg2) (clan) , and [Co (Hdmg) 2 (clan) 2]-

54CI are shown in ORTEP drawings in Figures 1, 2, and 3, re-

spectively. The individual bond distances for these three

compounds together with those of tv;o related compounds, C€Co-

(Il2dmg) (dmg) (sulfa) and [Co (Hdmg) 2 (an) 2] C^,^^ are tabulated

in Table 12. The corresponding bond angles are given in

Table 13.

In each case the tv;o dmg or dpg groups are approximate-

ly planar as demonstrated by the deviations from least-squares

planes in Tables 14-16. The dmg groups of each complex are

linked by two intramolecular hydrogen bonds (see Table 17)

.

As in the case of C^Co (H2dmg) (dmg) (sulfa) ''^ the hydro-

gen bridges between the dmg groups in C^Co (H2dmg) (dmg) (clan)

were found to be asymmetrical with both hydrogen atoms bonded

to the same dmg ligand. The 0(21)-H(B2) and 0(22)-H(Bl) dis-o

tances of 1.13(8) and 1.16(8) A, respectively, compared to

the 0(12)• •

•H(B2) and (11 )• • -H (Bl) distances of 1.36(8) and

o

1.37(8) A indicate the formulation H2dmg and dmg for the two

43

Table 10"

The Final Atomic Parameters for Nonhydrogen Atoms of [Co(Hdmg)2

(clan)2lC£.^

Atom

44

Table 10 - extended

^33 ^12 ^13 ^23

332(3) 226(12) 169(9) -43(6)

873(8) 451(29) 1194(26) 13] (15)

482(7) -1987(79) -431(28) -982(29)

57(1) 9(5) 11(4) -12(3)

57(1) 40(6) -20(4) 15(3)

45(1) 28(6) 30(4) -9(3)

47(1) 26(6) 30(4) -21(3)

41(1) 53(6) 7(4) -7(3)

47(2) 47(8) 27(5) -24(4)

63(2) -25(9) 59(6) -42(5)

72(2) -85(12) -3(8) -93(6)

49(2) 2(15) -11(3) -59(7)

51(2) -22(15) 64(8) ] (7)

52(2) -11(10) 36(6) -12(5)

52(2) 42(7) 73(6) -4(4)

46(2) 68(8) 5o(6) 6(4)

77(2) 12(9) 109(7) 16(5)

68(2) 68(11) 47(8) 75(6)

45

Table 1j .

Final Parameters for Hydrogen Atoms for [Co (Hdmg) 2 (clan)^^^'

Atom[Bonded to] Distance x y z B

H(B1)[0(12)] 1.07(3) -408(8) -35(4) -133(3) 5.5(0.8)

H(2)[C(2)] 0.85(3) 280(4) 321(3) 190(2) 3.5(0.6)

H(3)[C(3)] 0.91(4) 447(6) 361(4) 3C6(3) 6.0(0.8)

H(5)[C(5)] 0.98(4) -92(6) 105(4) 431(3) 6.6(0.9)

H(6)[C(6)] 0.96(3) -248(5) 73(3) 244(.?) 3.9(0.6)

H(7)[N(1)] 0.88(2) -299(4) 146(3) 64(2) 2.1(0.5)

H(8)[N(1)] 0.94(2) -52(4) 262(3) 49(2) 2.7(0.5)

H(11)[C(13)] 0.90(4) 349(6) 440(4) -131(3) 5.7(0.8)

H(12)[C(13)] 0.89(4) 417(7) 315(5; -185(4) 9.0(1.2)

H(13)[C(13)] 0.91(4) 513(6) 353(5) -67(3) 7.3(1.0)

H(14)[C(14)] 0.86(4) -181(7) 217(5) -314(3) 9.0(1.2)

H(15)[C(14)] 0.80(5) -14(8) 300(6) -274(4) 10.0(1.3)

H(16)[C(14)] 1.01(5) -213(8) 337(6) -252(4) 11.0(1.4)

•

^The hydrogen atom is given follov7ed by the atom to which it

is bonded in brackets, the corresponding bond distance (A)

,

the positional parameters with estimated standard deviations(x lO"*"-^) , and the isotropic thermal parameters (a2) .

un o

•H -P

0)

o

cQ)

Q)

U XI•HE 0)

O >

n3 .c;

CU Ifi

£ <u

tri UC 0)

•H .Hoeo

x:

Cn

Q)

O 4->

(N (tj

K SH CN

• 'CQ) ^ CM C nJ

^ nj

Cn>H WH o e

-^ o^ -p

— <D^ 0^ty> Of: UTJ Ti<N>i

O <U

O XI=v> Eh

UH-4 •

o w

c o•H W

(0 --H

U <-i

E-«

>iP

i5 p o

47

(0 0)

-Pb- -PC -I

o

c

•HV^

Ct

u o•H >E ««

o x:+j

(d Q)

Ox: o-p o

tP o

•H

o oXi intn W\xi U

CM OlO'd

0) w d

3 oCri • CO

P4 r-' O

rH mV— Ci^ 0)

tT" OD. Wfa ^oCM >i

O Ci

u .a

u

O CO

Tltn-iH

f-; o

? fi.

CUP5 HE-i (fl

f^ EO V^

O

< -P

49

g0)

Xi+»

•ocId

cHd)

51

52

Tabic 12

Selected Interatomic Distances (X) in Some CobaloximeComplexes with Their Estimated Standard Deviations.^

C£Co(H2dmcj) (clan) C-CCo (Il2dpg) 2 (clan)

Co-N{l)

53

Table 12 - extended

C£Co(H2dmg2)(sulfa) '^ [Co (n2ding2)(clan) 2] C£ [Co (H2dmg2)(an) 2] C£

2.023(8) 2.003(2) 2.001(5)

1.870(8) 1.906(2) 1.885(6)

1.884(8) 1.889(2) 1.889(5)

1.323(11) 1.340(3) 1.353(6)

1.344(11) 1.362(3) 1.333(6)

1.289(14) 1.299(3) 1.286(10)

1.293(13) 1.290(3) 1.303(10)

1.494(16) 1.477(4) 1.463(7)

1.532(17) 1.483(4) 1.482(12)

1.488(16) 1.485(4) 1.476(11)

2.507(11) 2.495(3)* . 2.491(8)*

1.50 1.44(3) 1.29

1.60 1.07(3) 1.21

2.235(3)

1.905(8)

1.896(8)

1.326(10)

1.338(11)

1.292(12)

1.290(14)

1.447(17)

1.494(17)

1.488(16)

2.479(11)

0.90

1.04

54

Table 13

SG^o.oted Intramolecular Angles (°) in Some Cobaloximo Complexes

with Their Estimated Standard Deviations.^

C^Co(H dmg2) (clan) C£Co(h2dpg2) (clan)

N(l)--Co-N(ll) 90.5(2) 94.8(4)

N(l)-Co-N(12) 91.5(2) 92.1(4)

N(l)-Co-N(21) 88.4(2) 87.1(4)

N(l)-Co--N(22) 88.6(2) 88.6(4)

N(ll)-Co N(12) 82.6(2) 81.3(4)

N(ll)--Co-N(22) .98.8(2) 100.0(4)

N(ll)-Co-N(21) 178.8(2) 177.5(4)

N(12)-Co-N(21) 98.1(2) 97.0(4)

N(12)-Co-N(22) 178.6(2) 178.5(4)

N(21)-Co-N(22) 80.6(2) 81.7(4)

C£(l)-Co-N(ll) 90.6(2) 87.7(3)

C^(l)-Co-N(12) 90.6(2) 89.1(3)

C£(l)-Co-N(21) 90.5(2) 90.4(3)

C£(l)-Co-N(22) 89.4(2) 90.2(3)

cr.(l)~Co-N(l) 177.8(2) 177.4(3)

Co-N(l)-C(l) 119.7(4) 118.6(8)

Co-N(ll)-O(ll) 121.9(4) 123.3(7)

Co-N(12)-O(12) 122.2(4) 121.2(8)

Co-N(21)-O(21) 123.2(4) 123.5(8)

C;o-N(22)"0(22) 123.3(4) 120.7(7)

Co-N(ll)-C(ll) 116.0(4) 116.7(8)

Co-N(12)-C(12) 115.6(4) 114.1(9)

Co-N(21)-C(21) 116.6(4) 116.8(8)

Co-N(22)-C(22) 117.0(4) 117.4(8)

0(11)-:](11)-C(11) 122.1(5) 119.7(9)

0(12)-N(12)-C(12) 122.3(5) 123.8(11)

0(21)-N(21)-C(21) 120.3(5) 119.4(10)

0(22)-N(22)-C(22) 119.8(5) 121.7(10)

N(ll)-0(11) -0(22) 99.7(3) 95.9(6)

N(12)-0(12)-0(21) 99.7(3) 99.2(7)

N(21)-0(21) -0(12) 96.9(3) 98.2(7)

N(22)-G(22) -0(11) 96.0(3) 100.1(6)

55

Table 13 - extended

46 52C£Co(H dmg2)(sulfa) [Co (H2dmg2)(clan) 2] C^ [Co (H2dmg2)(an) 2] C£

90.5(3) 89.8(1) 91.5(4)

91.7(3) 93.2(1) 93.0(5)

89.3(3)

87.8 (3)

82.0(4) 80.8(1) 80.8(3)

98.7(4)

179.3(4)

98.7(3)

179.2(4)

80.6 (3)

89.6(3)

88.5(3)

90.5(3)

91.9(3)

179.7(2)

119.1(6) 119.7(1) 119.5(7)

123.0(6) 121.3(1) 121.4(6)

122.6(6) 122.7(1) 122.9(7)

121.6(6)

123.6(6)

116.4(7) 116.9(2) 116.0(9)

117.4(7) 117.7(2) 117.8(9)

116.3(7)

116.8(7)

120.5(9) 121.8(2) 121.8(12)

120.0(8) 119.6(2) 119.2(10)

122.2(8)

120.1(9)

98.3(6)

97.8(6)

99.2(5)

96.8(6)

56

Table 13 - continued

C£Co(H dmg ) (clan) C£Co(H2clpg2) (clan)

N(ll)

N(ll)

N(12)

N(12)

N(21)

N(21)

N(22)

N(22)

C(13)

C(14)

C(23)

C{24)

-C ( 1

1

-C(ll

-C(12

-C(12

-C(21

-C(21

-C(22

-C(22

-C(ll

-C(12

-C(21

-C(22

-C(12)

-C(13)

-C(ll)

-C(14)

-C(22)

-C(23)

-C(21)

-C(24)

-C(12)

-C(ll)

-C(22)

-C(21)

112.8 (6)

122.9(6)

113.1 (6)

122.5(6)

113.5(6)

112.4 (7)

112.3 (6)

123.2(6)

124.2(6)

124.4 (6)

124.1(6)

124.4 (6)

112.1(10)

125.6(11)

115.5(11)

119.5(11)

112.2(10)

120.9(11)

111.9(10)

126.0(11)

122.3 (11)

125.0(11)

126.8(11)

122.2 (10)

The atomic numbering of Co (H2dmg2) (an) 2c/* has beenchanged to correspoiid to that of compounds of this work.

57

Table 13 - continued - extended

C£Co(H2dmg2)(sulfa)'^^ [Co (H2dmg2)(clan) ^]Cl [Co (H2ding2)(an) ^]C.^^

113.3(9) 112.2(2) 112.4(10)

125.0(10) 125.0(2) 124.6(16)

110.7(9) 112.5(2) 112.2(9)

124.0(10) 124.1(2) 125.0(16)

113.1(9)

120.7 (10)

113.1(9)

122.9(10)

121.7(10) 122.9(2) 123.0(12)

125.3(10) 123.4(2) 122.9(13)

12 6.1(10)

123.6(10)

58

ligands. This is in contrast to results reported for various

Co(H2dmg2) complexes^^''*''' ''^' ^° ' '^^ as well as for Fo(H2dmg2)--

(imidazole) 2/^^ Ni (H2dm92) ,'"'^ and Cu(H2dmg2), where either

the hydrogen bridges were assumed to be equidistant from the

tv70 oxygen atoms or the ligands were monoprotonated. The

assumption of a symmetrical bridge may have in part been based

on the earlier TR spectroscopic work on M(H2dmg2) complexes

where the v^eak band due to nn O-II vibration near 1725 cm

was assumed to indicate a very sl)ort aiid symmetrical O-H-O

bridge. "^^'^^ McFadden and McPhail"'"'' reported the structure

of Co(H2dmg2) (CH3) (H2O) ii' which both bridging hydrogen atoms

if ordered are required crystallographi cally to be on one dmg

ligand. No comment" was made concerning the bridging hydro-

gen atoms.

Although both hydrogen bridges in C^Co {H2dpg2) (clan)

appear to be shifted toward one dmg v.'here the 0(21)-H(B2) ando

0(22)-H(Bl) distances are 1.16(10) and 1.17(15) Awhile the

0(12)--H(B2) and 0(11)-H(l!l) distances are 1.30(10) and 1.41

o

(14) A, the experimental uncertainty is too large to show

that result to be significant.

The hydrogen bridges in [Co (Hdmg) 2 (clan) 2] c£ are not

symmetrical and each dmg is singly protonated. The 0(12)-H(B1)

distance is 1.07(3) A and the (11) • • -H (bl) distance is 1.44

o

(3) A. The gross structure is very similar to that of

tCo(Hdmg)2(an) 2lC-^-

Bowman et al . suggested the N-0 distance to be a sen-

sitive indicator of the position of the bridging hydrogen.

59

Table 14

Deviations and Equations of Selected Least-Squares Planes

in C£Co(H2dmg) (dmg) (clan)^° +3

(a) Deviations (A x 10 )

Table 14 - continued

^The deviations of atoms used to define the plane aremarked with an asterisk.

GO

Plane

61

Table. 15Deviations and Equations of Selected Least-Squares Planes

ain C^.Co(H2dpg ) (clan)

° +3(a) Deviations (A x 10 )

62

Table 15 - continued

Plane 1 Plane 2 Plane 3 Plane 4

C(1B) 1094

C(2B) 1237

C(3B) 427

C(4B) -641

C(5B) -821

C{1C) 1232

C(2C) 1380

C(3C) 3C1

C(4C) -734

C(5C) -827

C(1D) 571

C(2D) 554

C(3D) -230

C(4D) -874

C(5D) -8^38

r p(b) Coefficients of the Plane Equation"^"

A>: + BY I- Cz " D

Plane

63

Table 16Deviations and Equations of Solected Least Squares Planesin po ( Hdmg ) ( c 1 an )2 ]Cl^

(a) Deviations (A x lO'*'"^ )

Co

0(11)

0(12)

N(ll)

N(12)

C(ll)

C(12)

C(13)

C(14)

N(l)

C(l)

C(2)

C(3)

C(4)

C(5)

C(6)

Cl{2)

Plane 1

64

XI

Q

VO VO >X> 00 CO ro CM (No n

VD

65

Dissimilar N-0 bond lengths should indicate the hydrogen is

not symmetrically located and is closer to the dmg with the

longer bond. This holds true in C£Co(H2drag) (dmg) (clan) where

the N-0 distances appear to be different. The N (21) -0(21)o

and N(22)-0(22) distances of 1.348(6) and 1.359(6) A in the

diprotonated dmg are longer than the N (12) -0(12) and N(ll)-o

0(11) distances of 1.329(6) and 1.337(6) A in the dianionic

dmg. Using the significance test described by Cruickshank

and Robertson the N (21) -0(21) distance is possibly longer

than the N (12) -0(12) with a t^ value of 2.2 4 and the N(22)-

0(22) bond is significantly longer than the N (11) -0(11) bond

with a t value of 2.59. Also, in [Co (Hdmg) 2 (clan) 2] C£ theo

N(12)-0(12) bond of 1.362(3) A is significantly longer thano

the N (11) -0(11) bond of 1.340(3) A, v/here the bridging hydro-

gen atom is bonded to 0(12). Neither the N-0 distances nor

the bridging O-H distances in c£Co (H2dpg2) (clan) are signi-

ficantly different. In [Co (Hdmg) 2 (an) 2] CZ where the hydrogen

atoms are not significantly removed from a symmetrical posi-

tion, the N (12) -0(12) distance is shorter than that of N(ll)-

0(11). The difference in these two bond lengths of 1.333(6)

and 1.353(6) A is of possible significance (t^ = 2.36). The

sensitivity of the N-0 bond as an indicator of the bridge

position is questionable. The N-0 bonds are not significant-

ly different in C'CCo(H2dmg) (dmg) (sulfa) when both bridging

hydrogen atoms are shifted to one dmg. In the closely rela-

ted dimethyl ( 3,3 '-trimethylenedinitrilo) bis- (butan-2--one-

oximato) cobalt (III) complex the two N-0 distances are e::ual

6C

even though an asyinmetric hydrogen bridge is clearly indi-

cated by the difference Fourier syntheses. Although a

difference in the N-0 bond lengths as a function of protona-

tion is reasonable, there are very few structures so precise-

ly determined that this comparison can be made. Hence, no

general conclusion may be made. Hov;evcr, when a significant

difference in the N-0 distances has been found and the bridg-

ing hydrogen atom has been precisely located, the hydrogen

atom is associated with the longer N-0 bond.

Another point in support of the formulation C£Co(H2dmg)-

(dmg) (clan) is the difference in the Co-N bond lengths. Theo

Co-N distances on the ll2dmg side are 1.908(5) and 1.906(5) Ao

compared to distances of 1.872(5) and 1.884(5) A on the dmg

side. The differences in the Co-N bond lengths are signifi-

cant and the shorter distances involve the dianionic group.

This holds true in the other cases where the presence of both

H2dmg and dmg ligands has been indicated. In CcCo (H2diTig) (dmg)

-

(sulfa) ' and in Co (H2dmg2) (CII^) (H2O) ^'" the distance.s from

the cobalt atom to the dianionic ligand are shorter than the

distances to the neutral H2dmg ligand. This is not the case

in C£Co (ri2dpg2) (clan) where the distances from the cobalt atom

to what would be the dpg didnionic ligand, 1.9 35(11) and 1.908o

(9) A, appear to be longer than the corresponding distances

to the n2dpg ligand, 1.887(10) and 1.897(9) A. These differen-

ces together with the apparent positions of the bridging hydro-

gen atoms (vide supra ) in C£Co(H2dpg2) (clan) are of question-

able significance.

67

For the mononegative ligands in [Co (Hdmg) „ (clan) 2] C^

the Co-N distances are significantly different. However, N(12)

which is l:ionded to the protonated oxygen atom is closer to the

cobalt atom than is K(ll) with distances of 1.889(2) and 1.906o

(2) A, respectively. The same relationship holds in Fe(?Idmg)2-

55(imidazole) 2 r the only other M(Hdmg)2 complex whose X-ray

structure precisely places one bridging hydrogen on each dmg

and shov/s a significant difference in the metal to nitrogen

distance.

/in unsyixmietrical hydrogen-bonding system involving two

similar atoms may be fluxional. In such a system two equili-

brium positions, i.e. potential v/ells, exist for the hydrogen

atom. Each of these positions may be considered as having tiie

hydrogen atom covalently bonded to one atom and hydrogen bon-

ded to the other. For the system to be truly fluxional the

energy barrier betv/een the tv/o positions must be thei:aally

accessible. Depending on the relative depths of the potential

wellr. , tlie energy barrier betv^een them, and the thermal ener-

gy of the system the position of the hydrogen atom as indi-

cated by X-ray diffraction experiments would vary. Because of

the diffuse appearance of the bridging hydrogen atoms of the

M(n2dmg2) complexes in difference Fourier syntheses, a fluxio-

nal system with two potential wells of unequal depth seems

reasonable. The relative populations of the two positions will

depend soniev7hat on the depths of the potential wells. The ex-

perimentally determined position (or positions) of the hydro-

gen atom v/ill reflect these populations. As the depths of the

68

potential wells approach equivalence and as the energy barrier

between them becomes smaller the position of the hydrogen atom

will become experimentally more uncertain. A fluxional sys-

tem could, in part, account for tlie difficulty iii precisely

locating the bridging hydrogen atoms in M(H2dmg2) complexes.

The orientation of the 4-chloroaniline ligand in the

complexes of this study is quite intriguing. A projected view

down the Co-N(l) bond for C£Co{H2dmg) (dmg) (clan) is shovm in

Figure 4. A similar view for [Co (Hdmg)2 (clan) 2] C£ is given in

Figure 5(a) and one for C^Co(H2dpg2) (clan) is given in Figure

5(b) . In CeCo(H2dmg) (dmg) (clan) , as in C£Co(H2dnig) (dmg) (5:.ulfa)^^

the aromatic ring of the aniline is oriented over the dianio-

nic dmg ligand. The orientation angle, i.e. the dihedral

angle between the planes having Co-N(l) in common with one

containing C(l) and the other containing the bisector of the

angle N (11) -Co-N (12) , for C£Co (K2dmg) (dmg) (clan) is 0.9° and

for C£Co(n2dmg) (dmg) (sulfa) is 1.8° us given in Table 18. In

[Co(Hdmg) 2(clan) 2]C£ and in [Co (Hdmg) 2 (an) 2]C£ the ben7ene

rings are skewed relative to the equatorial ligands with ori-

entation angles of 53.9° and 58.3°, respectively. It seems

significant that in the former pair of Co (H^dmg) (dmg) type

complexes the rings align while in the latter pair of Co (H-

dmg) 2 type complexes the rings are skewed. Although tho ben-

zene ring of the aniline is tipped from being parallel to the

dmg plane by ca. 30° as in other similar complexes (see Table

18) the alignment and the distances between the two planes in

C£Co(H2dmg) (dmg) (clan) suggest a ir-type interaction. The

o

-IC) CNu Ui

CP o-H u

CJ

MO

I

oo

ol-l

n)

0)

•H>

(U+)o0)•nOM&.

70

O

o-

CQ

.X

O

o

CM

ooo

XI

cnJ

=^CJ

o

(M

6in wQJ O

O

:3I

oo

OH

I

>

d(U-po0)

-nOU

72

73

en

ofH

c

E

o

u

o

CM

a,

KOOu

rHo

CM

o

10

74

0)

co

y,

I

00I-l

Q)

iH

aEH

<N

'd

O

uCM

rHo

•d(N

OU

o> o-i ^-^ Cf^

• • o •

(N 1X> CO >X)

rO OO rH CO

n00in

o r>- —

,

r-• • o •

CO CTi CO <Nn CO M 00

00

min

b->

75

distances from the dmg plane to C(l), C(2), and C{6) giveno

in Table 14 are substantially less then the 3.40 A interpla-

nar distance in graphite. A proton transfer occurring from

one Hdmg ligand to the other would increase the electron den-

sity within the ir-system of the formed dianion. An interac-

tion by v/hich the filled it orbitals of the dmg overlap v;ith

the empty ii* orbitals of the aniline v;ould enhance the basi-

city of the aniline ligand. The complex formed v;ould be stron-

ger than might be expected based on the K, value alone. This

same argument applies to C-£Co(H-dmg) (dmg) (sulfa) which was

the first example of ligand-induced proton shift in a mole-

cular complex. While the positions of the bridging protons

in C-^Co (H^dmg) (dmg) (clan) and [Co (Hdmg) 2 (clan) 2] C^ are well

defined, the bridge in C.£,Co (Hpdpg-^) (clan) is ill defined and

the orientation angle of 36.7° is an intermediate value (see

Table 18). The 0---0 distances in this complex shov; more

variation than those in other related complexes as sho\;n in

o

Table 12. The 0.08 A difference in the 0...0 distances is the

same as for the corresponding N-'-N distances. The N(12)'''

N(21) separation is 2.836(15) A and the N (11) ••

'N (22) dis-o

tance is 2.914(13) A. Concurring with these observed distan-

ces, the N(12)-Co-N(21) angle of 9 7.0(4)° is more acute than

the N(ll)-Co-N(22) angle of 100.0(4)°. None of tlie other com-

pounds examined shows any significant differences in the cor-

responding distances and angles between the diglyoxime li-

gands

.

76

A comparison of mean bondiny distances for each of the

reported Co(H2dmg2) complexes may be made from Table 19. There

appears to be little variation in the average Co-N distances

or in the average dimensions within the equatorial dimethyl-

glyoximc ligands as a function of the axial ligand.^

Those complexes having chloride as an axial ligand show

a definite variation with the nature of the trans ligand. The

longest Co-Ct distance is found where tpp is the trans li-

gand. This is not surprising since phosphines are knovm to

have a very large trans- influence but the small influence

the tpp ] igand exerts on the tran s -chlorine atom compared to

40that of an ammonia ligand is unexpected. There is no sig-

nificant difference in the Co-N(l) distance involving a clan

ligand v;hether it is trans to a chlorine atom or trans to

another clan ligand. The trans -influence appears to occur in

Co (K2dii-ig2) complexes but not to a large extent.

The Co-Y distances in the XCo(H2dmg2)Y complexes where

Y is a ligand with an sp nitrogen, increase in the following

order of Y: NH^ < an '>- clan < sulfa (see Table 19). This

series can be rationalized in terms of the relative K, 's for

sulfa (2.3 X lO"-*-^),^^ clan (9.6 x lO""'--'-),^^ aniline (4.0 x

10~ ),^^ and ammonia (1.3 x 10~) . Bruckner and Randaccio

did not consider the J'j-'s of the different nitrogen donors

in their argument of the trend in trans - influencing ligands,

X, upon the Co-N bond. The same Co-N distances were used for

NH^ and aniline complexes in their argument for basing the

extent of trans- in fluerrce on the a-donor power of the trains

77

U) i-H

u

C^

o n

OI

CO

<U

or-!

ou

IKO

I

ou

c

i~l

,Q —

(0

Q)

OGtH4JCO

HQ•Oc;

opq

o

Ho

-IJ

U-l

o

>.u

i

CO

I

ou

I

ou

IT)

CN

n

o ^--vo u~> (N

CO 0-)

en

78

0)'0ca)-p

y.

0\r-i

(1)

rH

aEh

(1)

UC<u

u0)

Q)

79

ligand as are presented here.

In comparing C-^Co (H2dpg2) (clan) with C-CCo (H2dmg) (dmg)

(clan) the distances from the cobalt atom to the equatorial

nitrogens in the H2dpg complex are longer and the distances

to the axial ligands are shorter in the same complex. Because

the phenyl substituents are inductively more electron with-

drawing than methyl groups , Hdpg should be a v/eaker Lev;is

base than iJdmg. The equatorial distances to the Hdpg should,

therefore, bo longer. From an electronic standpoint the co-

balt ion in the Hdpg complex would be more positively charged

and a better Lev;is acid toward the axial ligands than in the

Hdn^g complex. From a steric point of view the axial ligands

are afforded a wider path of approach and v/ill, therefore, be

closer to the central cobalt ion. v/hen the equatorial ligands

are farther away

.

The benzene rings in the clan ligands of Ci^.Co (IlTdmg^J "

(clan), C£Co (H2dpg2) (clan) , and [Co (Hdmg) 2 (clan) 2]CC are pla-

nar (see Tables 14-16) having average C-C values of 1.376(3),o

1.380(10), and 1.378(3) A, respectively, with individual

values reported in Table 20. The phenyl rings of the Hdpg li-

gands of C^Co (H2dpg2) (clan) are also planar with pertinent

values and equations of least-squares planes given in Table 21

The crystals of C-£Co (H2dmg) (dmg) (clan) are held together

by six hydrogen bonds where there are eight hydrogen atom.s

capable of hydrogen bonding. Relevant hydrogen-bonding data

are presented in Table 17. Although the 0-H---0 bridges be-

tween the H2d;ag and dmg groups are not synv.aetrical, th.-; O-II

80

o

-p

EH4J

U

V(

•H0)

x:

?

m(1)

Ho<D

iHos<u

r:

•H

•rH

c

o

o

oI

<1> nsr--| 0)

;Q -!->

fct C•H•ci

Xoou

o

(0

0)

<

co«

•si

uCM

c"

rHu

CM

KOU

r !

u

a,

CM

o<^u

U

e

KOuu

in

Id ;^

c; o(0

to

(U

oC (1)

«0 Q+t

W Ti•H H

-d ci

C To

o -n

« to

in

o<

Vc

Ptn

•HQ

"-f IT, Vi) »tf' ':? rO

roCOro

t-

r>-)

00 in oro

r-! r^ iH

r-i rHOCN

O rH(N CM

o a\£X> O(O •<-'

-^ rH r-l -I rH •1

CNm

o r- mCN] .H rH

(vj n' <.o e5 ^1

vo •>-j< r- o CMro 00 ro 'a* r-

CO CDor-l

o orH r-l

O -^ '-^

r-( CTN CX)

OT OO

o CO (» cyi '^r

r- CO r~ r- ro00 oo ro oo r-

i rH -1

I

'--1

t

m '3' in <x) rH ^-'

-' — -- — --' UC» U U U O 1

I I I I I'->

^^ ,-. ^~. c^r-i I-

:

<3< in "vO ^-^

?», C) a O CJ U

CN

81

Table 21

Bond Distances, Bond Angles, and Least-Squares Planes ofthe Phenyl Rings in C£Co (H2dpg2) (clan) with The.ir EstimatedStandard Deviations.

23 24(a) Distances

C{n)-C{lt)

C(n)-C{5.e)

C{ll)-C{2l)

C{2l)-C{3l)

C(3£)-C(4.£)

C(4^)-C(5^) .

(b) Angles (")

C(n-2)-C(n)-C(U)

C(n-2)-C(n)-C(5£)

C(n)-C(U)-C(2£)

C{ll)~C{2l)-C{3l)

C{2Z)-C{3l)-C(Al)

C(3£)-C(4l)-C(5£)

C(4£)-C(5£)-C(n)

C(5£)-C(n)-C(U)o

(c) Deviations (A

Rings

C(n)

C(U)

C{2l)

C(3l)

C{4l)

C(5^)

C(n-2)

n = 13£ = A

14B D

1.3G3(18) 1.411(20

1.421(20) 1.396(20

1.368(19) 1.371(20

1.370(21) 1.367(20

1.352(20) 1.391(23

1.37.1(20) 1.390(20

123.9(11) 119.3(12

119.9(11) 120.9(12

122.8(13) 120.6(13

119.5(13) 119.3(14

120.5(13) 121.0(14

120.0(14) 120.4(14

121.0(13) 118.4(14

116.2(12) 119.8(13

X

1.370(19) 1.426(17)

1.356(17) 1.458(18)

1.432(19) 1.385(19)

1.351(21) 1.401(20)

1.371(23) 1.397(20)

1.409(18) 1.397(18)

120.9(11) 121.7(11)

121.2(11) 120.6(11)

122.3(12) 122.6(12)

117.0(13) 117.7(13)

122.2(14) 122.5(13)

118.7(13) 120.2(13)

121.7(12) 119.0(12)

117.9(12) 117.7(11)

+ 310 ) from Least-Squares Planes of Phenyl

2

-7

10

-10

5

-2

-3

41

-14

-31

48

-20

-24

172

-3

8

15

-29

3

19

-16

3

-12

24

-28

20

-7

20

(d) Coefficients of the Plane Equation PX + QY + RZ = S

P Q R S

Phenyl A

Phenyl B

Phenyl C

Phenyl D

-0.5815

-0.4144

-0.6482

-0.1592

0.5296

-0.7511

0.3950

-0.8986

-0.6176

0.4990

-0.6509

0.4088

4.7459

3.1793

4.0341

1 . 3 6 ^: 2

82

distances arc longer than might be expected. The tv;o hydrogen

atoms on N(l) of the clan ligand both hydrogen bond to differ-

ent water molecules. The hydrogen atoms of one water mole-

cule, 0(w2), form reasonably strong hydrogen bonds to 0(12)

and C£(l) . The hydrogen atoms on 0(wl), however, have only

short contacts with angles indicating only v;eak hydrogen bonds.

V^hile [Codldmg) 2(clan) 2]C£ and C£Co (H2c3pg2) (clan) both

exhibit the hydrogen bonding botv.'een the equatorial ligands,

Ci^Co(n2dpg2) (clan) has no interraolecular hydrogen bonds. While

the hydrogen atom on the solvent molecule was not located, a

hydrogen bond may exist between 0(S1) and 0(22). Each mole-

cule of [Co(ndmg) 2 (clan) 2]C^ possesses two intermo] ocular hy-

drogen bonds. Each clan molecule shows a hydrogen bond from

N(l) to the 0(11) of another molecule. The other hydrogen on

each N(l) is hydrogen bonded to the ionic chloride. Relevant

hydrogen-bonding data for these two compounds are also presen-

ted in Table 17.

o

All intermolecular distances less then 3.6 A were cal-

culated and carefully examined. No unusually short intermole-

cular distances were found.

Ligand-induced proton shifts may be of biological sig-

nificance. Since proton transfers in living systems are rela-

tively comnon, the study presented here provides an impor-

tant examination of orientation effects and enhanced stabili-

ties which may be achieved by a small shift of one proton.

CHAPTER 5

A NOVEL BINUCLEATING LIGAND: THE CRYSTT^ AND MOLECULAR STRUC-TURES OF 1 , 4-DIHYDRAZINOPHTHALAZINEBIS (2-PYRIDINIUMCARBOXAL-DIMINE) NITRATE DIHYDllATE AND iJ-CHLGROTETRi^J'i.QUA [1 , 4-DIHYDRA-ZINOPHTHALAZINEBIS (2-PYRIDINECARBOXALDIMINE) ] DINICKEL(II)

CHLORIDE DIHYDRATE

Binuclear complexes of chelating ligands have been of

interest recently for their potential activation of other

6 8~ 7 3ligands at an accessible bridging site and for their mag-

netic properties.^'*''^^~^°

The structure of [Ni2C£{H20) ^.(dhph-

py)]Cl^ shows the planar chelating ligand, dhphpy, to be ca-

pable of binding two metal atoms simultaneously. In that com-

plex, a bridging site betv/een the nickel ions is occupied by a

chloride ion. Therefore, at lea-st one bridging ligand in addi-

tion to dhphpy may be accommodated by M2dhphpy complexes.

V7hile the study of magnetic interactions betv/een metal

ions through bridging atoms in svxch systems is convenient and

theoretically significant, the catalytic possibilities of this

type system are exceptional. The nitrogen- fixing enzyme nitro-

genase has been considered to contain a polynuclear active

•4. 6,7site. '

Although the mechanism of the reduction of N2 to KH^ by

nitrogenase is not understood N2 is believed to be coordina-

ted to the metal ions of the enzyme. ' ' Nitrogenase

has been shown to reduce a wide variety of small molecules

7which contain a triple bon i , The distance betv/een the rt'etal

83

84

ions should be of importance in the activation of tliose mole-

cules. In the complexes of Robson and coworkers and of

8 3Okawa et al . the metal-metal distance is essentially con-

trolled by a single bridging phenoxide ion. However, in dhphpy

complexes the metal ion separation is fixed at tx greater dis-

tance by the geometry of the chelating ligand. Therefore/ lar-

ger molecules which are reduced in the presence of nitro-

genase, e.g. N^, N^; ^2^* ^2'^2' ^"^ HCN, should bo suitable

for incorporation as bridging molecules opposite the N-IJ

bridge of dhphpy. The syntheses and X-ray structures of

H2dhphpy (NO^) 2-H20 and [Ni2C£ (H2O) ^ (dhphpy) ] Ci^, • 2H2O were

undertaken to examine the nature of the accessible bridging

site in coniplexes of this type ligand.

So3.ution and Re finemen t of th e Structureof H2dhphpy (N03)'2 • ^^2^

The direct method of syn^olic addition was ust-d in v;hich

the signs of tv/o hundred large E's v.'ere assigned. All four-

teen nonhydrogen atoms of the ligand within tlie asymmetric

unit were located in an E-map computed from the signed K

values. Two Fourier syntheses v.-ere used to validate the selec-

ted model, locate the remaining nonhydrogen atoms, and re-

fine the atomic parameters. The refinement is outlined in

Table 5. The observed and calculated structure factors are

given in Table B-3. The final positional and thermal parame-

ters are presented in Tables 22 and 23.

85

COCN

o

86

«

N

to

87

Solution and Refinement of the Structureof [Ni2Ct:(H20 ) 4 (dhphpy) ]C£-:;-2H20

The position of Ni(l) was determined from a sharpened

three-dimensional Patterson function. The positions of the

remaining atoms were determined in a manner analogous to that

used v;ith C^CoCH-dmg) (dmg) (clan) . After the hydrogen atoms

were located they were included in further refinement with

each having an isotropic thermal parameter one unit higher

than the refined isotropic value for the atom to which the

hydrogen atom v/as bonded. A sutrmary of the refinement is gi-

ven in Table 5. The scattering factors for the nonhydrogen

29atoms were from Hanson et a l . and the hydrogen scattering

30factors from Stewart et al . Lists of observed arid calcu-

lated structure factors are given in Table B-4. The final

positional and thermal param.sters are listed in Tables 24

and 25.

Results and Discussion

The atomic numbering and thermal ellipsoids of K2dhphpy"

(N02)2*2H20 are shown in Figure 6 and those of [Ni2Cc(H20)^

(dhphpy) ]C£2*2H20 are shown in Figure 7. Selected interato-

mic distances of both compounds are listed in Table 26 and

corresponding angles Z'-re given in Tables 27 and 28. Both com-

pounds crystallize v;ith the cationic complexes, their anions,

and water molecules linked in a three-dimensional hydrogen-

bonded network. The postulated hydrogen bonds in the struc-

tures are listed in Table 29. Diagrams illustrating the pack-

88

Tabic 24

The Final Atomic Parameters^ of the Nonhydrogen Atoms for

[Ui^Cl iU^O) 4 (dhphpy ) ] 0^3 . 2H2O

Atom e 11

Ni(l)

Table 24- extended

89

22 33 '12 '13 23

273(4)

90

Atom

Table 24 - continued

y 2 '11

C(12)

91

Table 24 - extended - continued

^22

92

CQ

vococccr. cof^oovorMvoinr-ion-^-^vokDin

<d

ON

fM

93

0)

C!

-HPCOO

in

rH

rt

N

>^

a)

od

+>

P

o

O <U

< coCO

ID Lf") in LO LD LO IT) r-~ r~

o

r^ A

95

k-^

rH rO

97

mwm)

"

98

o

99

CN tNo->

fs] o cN n o^ <Tv

O r~- CTv (Ti ^ ro

^ m en CO r^ c^

,-1 rH -H r-l rH iH

100

0)

H

EH

nJ

<N

CM

(1)

rH

c:

<

O+-'

rj —n

101

Table 28Selected Angles in [Ni2C£ (H^O) ^ (dhphpy) ] C^^ • 2il

Atom Angle Atom Angle

N(l)-Ni(l)-C£(l) 98.0(2) N

N(l)-Ni(l)-N(4) 76.8(2) N

N(l)-Ni(l)-2vI(10) 155.7(2) N

N(l)-Ni(l)-0(1) 91.1(2) K

N(l)-Ni(l)~0(2) 90.3(2) N

N(4)-Ni(l)-C^(l) 174. G(2) N

N(4)-Ni(l)-N(10) 78.9(2) N

N(4)-Ki(l)-0(1) 87.8(2) N

M(4)-Ni(l)-0(2) 91.1(2) N

N(10)-Ni(l)-C^(l) 106.3(2) N

N(10)-Ni(l)-O(l) 88.5(2) N

KM10)-Ni(l)-O(2) 89.6(2) N

0(1)-Ni(l)-Ci:(l) 90.9(2)

0(i)-Ni(l)-0(2) 178.0(2)

0(2)-Ni(l)-C£(l) 90.3(2)

N(10)"C(11)"C(12) 122.2(7) N

C(ll)-C(12)-C(13) 117.8(8) C

C(12)-C(13)-C(14) 120.3(9) C

C(13)-C(14)-C(15) 118.4(8) C

C(14)-C(15)~N(10) 122.3(8) C

C(15)-N(10)-C(ll) 119.1(7) C

N(10)-C(ll)-C(10) 116.2(7) N

C(12)-C(ll)-C(10) 121.6(7) C

C(ll)-C(10)-N(4) 114.7(7) C

C(10)-N(4)-N(3) 125.9(6) C

N(4)-N(3)-C(l) 115.3(6) N

N(l)-C(l)-N(3) 115.7(6) N

C(2)-C(l)-N(3) 122.7(6) C

N(l)-C(l)-C(2) 121.6(6) N

C(l)-N(l)-N(2) 121.8(6) C

C(l)-C(2)-C(7) 116.8(6) C

2)-Ni(2)-Ci(l) 97.8(2;

2)-Ni(2)-N(6) 76.5(2

2)~Ni(2)-N(20) 154.8(2:

2)-Ni(2)-0(3) 93.1(2:

2)--Ni (2)-0(4) 89.5(2:

C)~Ui{2)~Cl{l) 174.1(2:

6)-Ni(2)-N(20) 78.2(2:

6)-Ni(2)-0(3) 90.4(2:

6)-Ni(2)-0(4) 91.2(2:

20)-lii{2]--Cl{l) 107.5(2;

20) --Ni (2) -0(3) 88.3(2;

20)-Ni(2)-O(C) 89.8(2;

3)-Mi(2)"Cf-(l) 88.2(2;

3)-Ni(2)-0('0 177.2(2;

4)-Ni(?)-C,C(3) 90.5(2;

20)-C(21)-C(22) 121.9(7

21)-C(22)-C(23) 118.7(7;

22)-C(23)-C(24) 120. 2(P'

23)-C(24)--C(r:5) 117.7(8;

24)-C(25)-K(20) 122.6(7

25)-N(20)-C(21) 118.8(6;

20) -C (21) -C (20) 116.7(6;

22)-C(21)-C(20) 121.4(7;

21)-C(20)-N(6) 113.8(6;

20)-N(6)-M(5) 123.4(6;

6)--N(5)-C(£) 113.8(51

2)-C(8)-N(5) 116.3(6;

7)--C(8)-M(5) 121.8(6;

2)-C(8)-C(7) 121.0(6;

8)~N(2)-N(1) 120.8(51

2)-C(7)-C(a) 117.0(6;

102

Table 28 - continued

Atom Angle Atom Angle

C(l)-C(2)-C(3) 123.5(6) C (6) -C (7 ) -C (8

)

123.5(6)C(2)-C(3)-C(4) 119.7(7) C (5 ) -C ( G) -C (7

)

119.4(G)C(3)-C(4)-C(5) 120.1(7) C (4 ) -C (5) -C (6

)

121.6(7)Ni(l)-N(l)-N(2) 122.4(4) N.i (2 ) -N (2 ) -N (1) 123.3(4)Ni(l)-N(l)-C(l) 115.8(5) NJ.;2)-N(2)-C(8) 115.9(4)Ni(l)-N(4)~N(3) 115.9(4) Ni (2 ) -N (6) -N ( 5) 117.3(4)Ni(l)-N('l)-C(]0) 118.2(5) Ni(2)-N(6)-C(20) 119.1(5)Ni(l)-N(10)-C(ll) 111.9(1.) Ni(2)-H(20)-C(21) 112.1(5)Ni(l)-N(10)-C(15) 128.9(5) Ni (2) -N (20) -C (25) 129.1(5)Ni(l)-C£(l)-Ni(2) 98.4(1)

The estimated standard devjations are given in parentheses,

103

o

104

ing and hydrogen bonding in Il2dhphpy (NO-^) 2* 2H2O and in

[Ni2C£{Il20) 4 (dhphpy) )C£3-2H20 are presented in Figures 8

and 9.

The most noticeable difference in the structures of the

two dhphpy ligands is that H2dhphpy (NO-^) 2 * 2il20 contains a

tv/ofold rotation axis while the nickel complex docs not. In

both cases the ligand is approximately planar (see Table 30)

.

The nickel atoms and the bridging chloride of [hi.2Cl (II2O) ^-

(dhphpy) ]Cf o• 2H2O lie slightly "below" the least-squares

plane of the ligand (Plane 3) and both hydrazone portions are

pivoted generally about an N(3)---N(5) axis witli both C(14)

and C(24) "above" the plane. However, in the protonated li-

gand one hydrazone is pivoted "upv,ard" and the other "down-

v/ard" as required by the twofold axis. Also, the hydrazone

"arm5'. " in the nickel complex are drawn tov^ard each other com-

pared to the pro tone'! ted form as indicated by the bond angles

within the "arms." All of tl.e pyridine ringn are rotated

about tlje C(nO)-C(nl) bond relative to the phthala^ine plane

with the pyridine nitrogen atoms tipped toward the coordina-

ted species. In [Ni2C£ (lUO) . (dhphpy) JCZ^- 21I2O the pyridine

containing N(10) is rotated to a much greater extent than

that containing N(20). This is shov/n by tho deviations from

plane 4 (Table 30) of N(10) and C(12), 0.121 and 0.222 A,

compared to the deviations of N(20) and C(22), 0.148 ando

0.161 A. The rings of the phthalazine fragment in each com-

pound appear twisted relative to each other but by less

than 2".

n:l

106

Ui

•HI^ O

- u

... NN <- >s>1 +>> CM^<;\

P -

+to CN

rH

^r>

Pi

M

& =

o —

Ol (N ^d C

--, fj ,i^

o>i - Ma, N X),a I

^\^-- -re)•^ >i 0)^ + )->

O f^i fO

<N\ OtC- rH -fi— -T3

U 1

CSCM

u•J

•H

r-l

H2 r-^

o

6

V-l -^en:

•H --

'd o

CO

CO

a(1)

01ou

c In >irA -^^ l>iu

, -'drt! IX <U

4-> o<: fo a.

108

E •

o

109

o

0)

-Q

om

CM

o^a..c

c•H

(0

0)

C!

a

&<

u

toI

4J

WOj

<y

(Upo

O

C'-J

a

nU

<0

ro-1-

o

X '-

o

0) Men •

no um —

,

O a•H x:p cu(« X

W -si-

T) OC <Nnj K

C CJO <N•H -H•P J505 —

'

•H> T.5

0) CQ nJ

•H<-7

«0

OJ

nO

>1

a1:5

n

l-l

p-1

o-p

<

CD

o <; CM r--;

0)

C

rH

OP<

CM

rH

Q)

c

rH

o-p

<

I

I

f-J

r

4c

IT!

CjI

inI

I

CO

u

rH

roCM

I

rH rH

CN

o

V.0

i:>

ror-l I

oro

I

l-~ VD ID

C) u u

COt

4;

r-i

f- . C "I

u t_) r?.;

r-~ rHrH '-D

<T\

110

enin

1.11

All bonding distances involving nonhydrogen atoi/.s are

normal. The N-N distances in both compounds range fromo

1,363(7) to 1.374(4) A and are comparable to the N-N dis-

° 84tance in 4-FPYTSC of 1.36b (3) A, Since, this distance in

both the phthalazine and hydrazone groups is significantly

shorter than the accepted N-N single bond distance, 1.44±4

° 85A, and since the ligand is planar, a delocal3.zed system

is presumed to exist. In agreement with this assumption the

C(nO)--N distances are longer than the pure C--N double bond

distance and are all equivalent to the related C-N distanceO O A

in 4-FPYTSC, 1.275(3) A."" All other distances within the

ligand are not significantly different from those in [Ni(dh-

ph) (H^0)2C^^ -21120.^^

All Ni-N distances in [Ni^C-f. (H^O) ^ (dhphpy) ] Cf.3- 2H2O are

within the range of reported bonding distances of nickel (II)

with aromatic nitrogen atoms (2.00 to 2,112 A).

The bridging chloride is not symmetrically located be-

tween the two nickel atoms with Ni-'C-£ di.:;t3nces of 2.374(2)o

and 2.387(2) A. The appearance of this bridge is remarkably

similar to that in di-y-chloro- sym- trans-dichlorobis- (2,9-

p odimethyl-l,10-phenanthroline) dinickel (II) • 2chloroform

where the Ni-C distances are 2.378(3) and 2.394(3) A. Also,

the Ni---Ni distance, 3.602(2) A, and Ni-cC-Ni angle, 98.0(1)°,o

in that compound are equivalent to the 3.603(1) A separation

and 98.36(7)° angle in [Ni2C£ (H2O) g (dhphpy) ] 0^3 • 2H2O. This

distcince betv/een the nic}:el citoms is somewhat shorter than

112

the 3.791(4) 7v distance found in the [Ni (dhph) (H2O2] 2C^4

*

2H,.0 complex reported by Andrew and Blake where both

bridges are phthalazinc nitrogen atoms. The separation be-

tween the nickel atoms in the dhphpy complex, however, is

o

substantially longer then the Ni''-Ni distance of 2.879 A

in the doubly oxo-bridged complex of Hoskins, Robson, and

7nSchaap. All these inter-nickel distances are much greater

than tv;ice the covalei;t radius of nickel and must be a func-

tion of the bridging atomj.

The distorted octahedral coordination geometry about

each nickel atom in [Ni^Ci^ (1120) ^ (dhphpy) ] C>e3- 2H2O is comple-

ted by two v:ater molecules which lie on a line almost perpen-

dicular to the llgand plane. The Ni-0 bond distances are

87typical for water coordinated to nickel (11) ranging from

2.070(G) to 2.117(G) A.

A degree of uncertainty exists concerning the poiitJ.ons

of hydrogen atoms abouL 0(1) in Il2dl]phpy (NO^) 2 * 2H2O. Theo

0(1) -n(l) distance appears to be very short, 0.78 A, whileo

the N(10)-H(py) distance appears to be very long, 1.21 A.

Although the locations presented for the hydrogen atoms are

the most reasonable interpretation of the difference map in

terms of rcrk heights, distances, and M-O-H angles, other

areas of positive density exist about the N(l), 0(1) , and

N(10) positions. Disorder may exist with alternate forms ha-

ving N(l) protonated or having a "coordinated hydronium ion."

Complexes of dhph:y structurally provide a promising

113

uni-iuolecular system for the incorporation of a small mole-

cule at a bridging position. Dinitrogen has been reported as

a bridging ligand connecting two metal complexes in the

y-dinitrogen-bis{ [1, 2-bis (dimethylphosphino) ethane] hydrido-

[q- (1/ 3, S-trimethylbenzene) jmolybdenum} cation ard similar

89compounds. No complex has been reported which could retain

its structural integrity after the removal of a bridging di-

nitrogen. The structures presented here suggest complexes of

ligands similar to dhphpy may have such a capacity.

CHAPTPjR 6MODELS OF PROPOSED INTERMEDIATES FOR THE CATALYZED CYPT T-ZATION OF ACETYLENES: THE CKYST/iL AND MOLECULAP STRUCTUPFqOF l-(Tr-CYCL0PENTADIENYL)-l-TRIPHi^NYLPII0SPIiINE-2 3 ^

^^"-'^^^^

TETRAKIS{PENTAFLU0R0PHENYL)C0RALT0LE AND 1- (tt -CYCLOPFNTADIENYL) -l-TRIPHENYLPIIOSPIJINE-2 ,3 , 4 , S-TETFJ^KIS (PENTAFLuiRO-

PHENYL) RHODOLE

The catalysis of tho oligornorization of acetylenes by

tran.sition metal complexes has been extensively studied. ^^

A reaction mechanism involving a metallo-cyclopentadiene

intermediate has been suggested^"^^ for the trimerization of

two molecules of acetylene v^ith one of olefin in the pre-

scencc of NiBr^Ctpp)^, Ni (CO) ^ (tpp) 3, and ether nicJ.el cat-

alystF:. Metal-containing hererocycles, metallocycles, have

been implicated^^" ^^"^^as intermediates in the react: onr. of

acetylenes v/ith Tr-cycIopentadienyJdicarbonyl-metal complexes

in which the metal was cobalt, rhodium, or iridium. Yamazaki

et_ea. on the bar.is of chemical reactions assigned a

metallocyclic structure to a phosphine-containing cobalt

complex isolated from the reaction of diphenylacetylene withCo(cp) (tpp)!^ and isopropylmagnesium bromide. They also

isolated the same product from the reaction of excess

diphenylacetylene with Co(cp) (tpp)^. A preliminary report

of the structure of a cobaltacycle formed by the reaction of

Co(cp) (tpp) (PhCiCCO^Me) with dimethyl maleate has been

reported.

114

115

15Rausch and Gastmger prepared C. (f ph) .Co (cp) (tpp) by

the reaction of bis (pentafluorophenyl) acetylene with r-cyclo-

pentadienylcarbonyltriphenylphosphinecobalt. The analogous

rhodium compound was prepared by the reaction of the corre-

15spending rhodium compound.

9 7Except for one preliminary report no structural data

have been available for cobaltacyclopentadiene metallocycles.

Therefore, the X-ray diffraction stjrucLural analysis of

C. (fpii) 4C0 (cp) (tpp) v/as undertaken. The corresponding rhoda-

cycle was studied for comparison with this cobaltacycle and

related compounds.

Structure Solution emd Refinevaentfor C4 (fph) 4Co"(cp) (tpp)

~

The heavy atom method was used in vjhich the positions

of the cobalt and phosphorus atoip.s were estimated from a

sharpened Patterson function. A Fourier synthesj.s based on

these atoms v/as used to estimate the positions of eighteen

additional atoms. Successive Fourier syntheses revealed the

locations of all nonhydrogen atons in the c;ompound. A differ-

(Bnce Fourier synthesis at that point revealed a region be-

tween the cobaltacycles which v;as of relatively high electron

density. Because this density v/as diffuse no additional ato-

mic positions were estimated before starting refinement, R =

0.27. Three cycles of least-squares refinement with indivi-

dual isotropic theriual parameters reduced R to O.l'l. A differ-

ence Fourier synthesis again revealed relatively high eloc-

116

tron density in the same location as Lefore.

Because of the discrepancy of the calculated density

3 3(1.423 g/cm ) from the measured density (1.59 g/cm ), solvent

molecules were presumed to be in the crystal. The deep red

14crystals of the compound were grown from Skelly C which is

a saturated hydrocarbon fraction boiling betv.'een 88 aiid 9 8°C

and consisting mainly of n-heptane,^-j^^i^'

^^ two solvent

molecules were in the unit cell the calculated densiity would

3be much nearer the measured value at 1.55 g/cm . Several

maxima were observed in the difference Fourier synthesis v/ith-

in the region of high electron density. The distances between

these points and the angles made by lines connecting them did

not reasonably approximate a hydrocrirbon chain.

The thermal parameters were converted to their aniso-

tropic equivalent and nine least-squares cycles using a block

approximation to the matrix reduced R to 0.077. The sliifts

of all parameters during the fineil cycle were less than one-

tenth of their resi^cctivc estimated standard deviations. A

difference Fourier synthesis calculated at this stage again

suggested the presence of an ill-defined solvent molecule.

Although the distribution of the peaks, which were not v;ell

resolved, suggested a C-, oi' Cg chain, a closer examination of

the distances and angles within the group shov.'cd them not to

reasonably approximate a hydrocarbon chain.

Six peaks were selected which closely retained their

positions in the final ?'ourier summation before refinement

and in the difference Fourier syntheses just discussed and

117

which seemed the most reasonable in approximately a hydrocar-

bon chain. These locations were used isotropically as carbon

atoms together with the seventy-three refined positions from

the third full-matrix least-squares cycle used anisotropical-

ly in a structure factor calculation and in three cycles of

block approximation least-squares refinement. Although almost

all the poorly matched reflections (|FqV)^ - ^Valc^'*^^^^^~

proved, a Fouiier synthesis revealed peaks at positions shif-

ted to a less reasonable distribution from the linear hydro-

carbon approximation used. The refinement was terminated at

this point. An outline of the refinement is presented in

TaDle 5.

Scattering factors for cobalt, phosphorus, fluorine,

29oxygon, and carbon v;cre taken from Hanson c t a ]. . A list of

14observed and calculated structure factors is available.

Structure Solution and Refi.neiuentfor C4 { fph) 4lZh (cp) (tpp)

The method of isomorphous replacement was used for the

solution of the structure of C. (fph) ,Rh(cp) (tpp) . The cell

constants of C^ (fph) .Co (cp) ( tpp) and C^ (fph) 4Rh(cp) (tpp) as

reported in Table 4 are very similar with differences of less

than one percent. The positional parameters from the third

cycle of full-matrix least-squares refinement for trie non-

hydrogen atoms in the isomorphous compound C. (fph) 4Co(cp) (tpp)

were used in a structure factor calculation and a difference

Fourier synthesis with the C^ (fph) ^P.h (cp) ( tpp) data. The

structure factor calculation res\iltod in an R of 0.17 and the

118

difference Fourier synthesis revealed no major structural

differences in the tv;o compounds. The same positional para-

meters were used in an isotropic least-squares refinement of

the C, (fph) ,Ill-i(cp) (tpp) data. A summary of further refinement

is given in Table 5.

A difference Fourier synthesis after refinement suggest-

ed the presence of an ill-defined solvent molecule. As in the

3case of the" cobaltacycle the calculated density, 1.47S g/cm ,

3is significantly less than the density of 1.60 g/cm obtained

from flotation measurements of the yellow crystals. If two

molecules of n-heptane are assumed within the unit cell the

3calculated density v;ould be 1.60 g/cm .

An attempt to fit a linear molecule to peaks in the

difference Fourier synthesis was also unsuccessful and was

not pursued.

The scattering factors used v.-ero taken from Hanrion

29et al . Tlic observed and calculated structures are listed mTable B-5.

Results and Discu ssion forC4{fph) ^Co(cp) (tpp) and C4 (f ph) 4Rh (cp) (tpp)

The. final positional and thermal parameters for the.

nonhydrogen atoms of both C. (f ph) .Co{cp) (tpp) and C^(fph)^-

Rl-i(cp) (tpp) are listed in Table 31. The atonic numbering and

thermal ellipsoids of the cobaltacycle are shown in Figure 10.

The atomic numbering of the rhodacycle is analogous. Selected

bond distances and angles for the two compounds are listed

119

1

120

CO

121

CM

ca

122

ca

CQ

CM

CQ

>-.

N

00 00 c—I CT*

o o ro 'T m "^cr\ i-H r~- r^ vd vd

CM IT)

f-{ o

r- r^

vD inin r^ OS in

O i-{

in nCTl rH in in

CM inin v£)

00 00

cH rH

rH r-. in t—in T

rH orH rH

r-\ rH vr in•-t r-l

in V.O n P-) O rHrH t-A

^^ O rHr- r~ rH r-l rH rH CTl CT\

VD in

VD VD

CO r-VD in

o inin •<3'

r~t -^ VDCD 00 o r- VD

CTv VD O CMO CTl

rH rH

vf o.en CN

m

123

124

ca TiBu

4J

d0)

•H

0)4J-P•iH

o

(i)

>

to

C

5^

O

X! ^ in+J -P O

u

o

0/

o

d d(&

'J

4J Q)

om 00

D^—d U•HM "-d

dt-i (ti

fci

ou

0) ^^ o

oa)

y^ '

,d —p-a* a

o--

. - x; oXI w -Pa, trs w«n d "> r^i— -H >i o

x; 1T3

o ^ -^

d -d wu

n-d

wEh

a;oc

"d

oto

r-i O

0)

. -d

do

x:-p•H

126

127

in Tables 32 and 33. Least-squares planes and deviations are

given in Table 34.

The molecules are metallocycles with the metal atom also

bonded to the cyc]opentadienyl ring and to the triphenylphos-

phine ligand. The C(l) to C{4) fragment in both compounds is

planar with the largest deviation from the best plane being

0.015 A in the cobalt compound and 0.017 A m the rhodium

compound. The metal atoms, however, are significantly dis-

placed from the plane in the direction of the cp ring by

-0.203 and -0.239 A. This perpendicular displacement is simi-

9 8lar to that found in other similar metallocycles.

The metallocycles may be considered as a dolocalized

diena with the metal atom a-bonded to the two carbon atoms

of the ring, C(l) and C(4). The Co-C bond distances, 1.995

(11) and 1.993(11) A, and the Rh-C bond distances, 2.060(12)

and 2.067(11) A, are similar to various values given by

Churchill. ^^ Values of 1.979(1) A"''^ and 1.990(5) A^ have

more recently been reported for Co~C bonds in ccbaloxime

complexes. Mague '^"'^'^ has reported structures of similar

rhodacyles in which the Rh-C distances are 2.000(11), 1.964

(11), 2.047(16), and 1.998(16) A. Also, Cotton and Normano

report a singi.e-bcnd covalent radius of 1.39 A for Rh(ITI).

When this value is added to half the 1.485 A suggested length

for a single-bond between sp carbon atoms the Rh-C dis-

o

tance is predicted to be 2.13 A. The observed Rh-C distances

where rhodiuj.i has a formal oxidation number of ^•l are shorter

than r.he abc/e prodicted single-bond distance. T'ais iliffer-

128

Talkie 32Selected Bond Distances (A) of C^ (f ph)^M(cp)(tpp) (M=Co,Rh)with Their Estimated Standard Deviations in Parentheses.

M = Co Rh

M-C(l) 1.995(11) 2.060(12)

M-C(4) 1.993(11) 2.067(11)

H-P 2.234(3) 2.293(2)

M-C(51) 2.157(12) 2.286(13)

M-C(52) 2.121(13) 2.261(14)

M-C(53) 2.119(11) 2.250(13)

M-C(54) 2.104(9) 2.238(10)

M-C(55) 2.133(12) 2.268(12)

C(l)-C(2) 1.326(15) 1.343(16)

C(2)-C(3) 1.467(16) 1.457(16)

C(3)-C(4) 1.335(15) • 1.354(15)

C(l)-C(ll) 1.487(16) 1.498(17)

C(2)-C(21) 1.523(16) 1.497(16)

C(3)-C(31) 1.481(15) 1.478(16)

C(4)-C(41) 1.493(16) 1.492(17)

P-C(60) 1.848(11) 1.858(12)

P-C(70) 1.843(11) 1.821(10)

P-C(80) 1.834(12) 1.820(13)

C(51)-C(52) 1.463(20) 1.429(22)

C(52)-C(53) 1.400(15) 1.420(17)

C(53)-C(54) 1.426(18) 1.424(20)

C(54)-C(55) 1.433(16) 1.422(17)

C(55)-C(51) 1.457(17) 1.431(18)

129

Table 33

Selected Bond Angles (°) of C4 (fph) 4M (cp) (tpp) with Their

Estimated Standard Deviations Given in Parentheses. (M=Co,Rh)

M = Co Rh

M-C(l)-C(2) 112.1(8) 115.5(8)

C(l)-C(2)-C(3) 116.8(9) 114.9(9)

C(2)-C(3)-C(4) 114.8(9) 115.5(9)

M-C(4)-C(3) 113.1(7) 114,8(8)

C(l)-M-C(4) 82.4(4) 78.3(4)

P-M-C(l) 103.0(3) 101.6(3)

P-M-C(4) 95.2(3) 93.3(3)

C(ll)-C(l)-M 127.0(7) 123.3(8)

C(ll)-C(l)-C(2) 119.6(9) 119.4(10)

C(21)-C(2)-C(l) 123.9(9) 124.1(10)

C(21)-C(2)-C(3) 119.2(9) 120.9(9)

C(31)-C(3)-C(2) 119.7(9) 119.7(9)

C(31)-C(3)-C(4) 125.5(5) 124.9(10)

C(41)-C(4)-C(3) 119.8(9) 120.3(9)

C(41)-C(4)-M 127.0(7) 124.9(7)

C(51)-C(52)-C(53) 108.1(11) 108.3(12)

C(52)-C(53)-C(54) 109.6(10) 108.8(11)

C(53)-C(54)-C(55) 107.7(10) 106.9(11)

C(54)-C(55)-C(51) 108.0(10) 109.3(11)

C(55)-C(51)-C(52) 106.3(10) 106.8(11)

130

Table 34

Deviations from and Equations of Some Lease-Squares Planes ofC4(fph)^Co{cp) (tpp) and C^ (fph) ^Rh (cp) (tpp) .^

° +3(a) Deviations {h x 10 )

Atom

131

ence could be indicative of multiple bonding between the ter-

minal carbon atoms of the diene and the metal atom. The C-C

distances in the metallocycle rings fall into tv/o groups. The

C(l)-C(2) and C(3)-C(4) distances are equal within experimen-

tal error to the accepted value of 1.337(6) h for a simple

C-C double bond. The C(2)-C(3) distances are indicative of

a C-C single bond between tv.-o double bonds. The observa-

tions of Mague ' on tvi/o rhodacycles suggested a double-

bond system similar to those in C^ (fph) ^Co (cp) (tpp) and C^

(fph)4Rh(cp) (tpp) .

The cp rings in the compounds arc planar v;ith the maxi-

mum deviations from the least-squares planes of -0.016o

and -0.012 A. The distances from the cp ring atoms to the

metal atom shov/ that the metal atom is slightly displaced

from the center of the cp ring. The range of the Co-C(cp ring)

distances is from 2.104(9) to 2.157(12) A v;ith a mean of 2.127o

(9) A. These values are similar to those in other Co-cp

complexes. ^05,106

In both the cobalt and rhodium compounds the longest

metal-C(cp ring) distance involves C(51), the carbon atom

nearest the phosphine ligand. The mean Rh-C(cp ring) distanceo

is 2.286(13) A. This value is equivalent to the mean distance

of 2.246(9) A in Rh (C2F5) (cp) I (CO)"^^"^

and falls within theo

2.19 to 2.26 A range reported for corresponding mean values

for other cp- rhodium complexes.

The C--C bond distances v/ithin the cp rings range from

1.400(16) to 1.463(20) A with a mean of 1.436(11) A in the

132

cobalt, compound and a range from 1.420(17) to 1.431(18) Ao

with a mean of 1.4 25 A in the rhodium compound. These C-C

distances are comparable to those found in other cp com-

plexes. ' The cp rings are tipped relative to the

C(l) to C(4) planes by 35.3^ and 36.6°.

o

The Co-P distance of 2.234(3) A is similar to the Co-P

distance in five-coordinate complexes of cobalt where the

no ^

range is reported " to be from 2.152(G) to 2.27(1) A. Also,

in cobalt-carbonyl complexes such as Co^ (CO) • « (Ph2PCiCCB'2)2

and Co(CO) -;,(N0) (tpp) the Co-P distances are 2,236 and 2.229

A-'--'--' Jn the former and 2.224(3) and 2.230(3) A-*"""-^ in the lat-

ter. The Rli-P distance of 2.293(3) A is similar to those in

113phosphine complexes of rhodiura(I) .

' The metal to phosphine

distance in metal-oxime complexes have been found to be some-

40 97v/hat longer, ' The Co-P distance in cobaloximc complexes

has been reported as 2.327(4) h^^ and 2.339(1) A.^^ The PJi-P

° 102distance in RliC-£<Hd!ng) 2 (tpp) was reported to be 2.327(1) A.

Since the distances in oxime comj:>loxes in both cobalt and

rhodium are equivalent, the phosphorus atom may be in the

position of closest approach to the metal atom as limited by

the steric constraints of the oxime ligands.

The distances in the fph rings have been summarized in

Table 35. The individual values for the distances and angles

in the fph rings on the metallocycles and the phenyl rings of

the phosphides are given in Tables 36-38. The dimensions are

not unusual and are in agreement with expected values.

133

-p

D4

o<

-G

134

Table 36Bond Distances and Bond Angles of Pentaf luorophenyl Groupsin C^ (fph)^Rh(cp) (tpp)

.

o

(a) Distances (A)

n = 1 2 3 4

Cnl-Cn2 1.384(15) 1.342(16) 1.392(15) 1.385(15)

Cn2-Cn3 1.364(20) 1.400(20) 1.374(20) 1.351(20)

Cn3-Cn4 1.375(18) 1.358(18) 1.357(19) 1.389(18)

Cn4-Cn5 1.367(19) 1.365(20) 1.368(18) 1.355(19)

Cn5-Cn6 X. 372(20) 1.373(19) 1.367(18) 1.362(19)

CnC-Cnl 1.393(15) 1.389(14) 1.389(16) 1.386(14)

Cn2-Fn2 1.347(12) 1.354(12) 1.351(13) 1.344(12)

Cn3-Fn3 1.339(15) 1.341(18) 1.349(15) 1.348(16)

Cn4-Fn4 1.338(18) 1.337(19) 1.335(18) 1.340(18)

Cn5-Fn5 1.343(15) 1.358(14) 1.338(15) 1.357(14)

Cn6-Fn6 1.331(13) 1.343(14) 1.351(13) 1.342(13)

(b) Angles (°)

Cnl-Cn2-Cn3 123.1(11) 122.4(12) 123.7(11) 122.9(11)

Cn2-Cn3-Cn4 119.6(13) 119.3(13) 113.8(13) 120.2(13)

Cn3-Cn4-Cn5 119.6(13) 119.3(14) 120.8(13) 117.9(13)

Cn4-Cn5-Cn6 119.8(13) 120.6(13) 119.0(12) 121.4(12)

Cn5-Cn6-Cnl 122.6(12) 121.1(11) 123.6(11) 122.0(11)

Cn6-Cnl-Cn2 115.3(11) 117.3(11) 114.1(10) 115.4(10)

Cn -Cnl-Cn2 124.2(10) 123.9(10) 123.1(10) 124.1(10)

Cn -Cnl-Cn6 120.5(10) 118.8(10) 122.5(10) 120.5(10)

Fn2-Cn2-Cnl 120.2(10) 121.3(11) 118.2(10) 119.4(10)

Fn2-Cn2-Cn3 116.7(11) 116.4(11) 118.0(11) 117.7(11)

Fn3-Cn3-Cn2 120.9(12) 120.7(13) 120.3(12) 120.8(12)

Fn3-Cn3-Cn4 119.5(12) 120.0(13) 120.9(12) 119.0(12)

Fn4-Cn4-Cn3 120.7(13) 121.3(14) 119.9(13) 119.9(12)

Fn4-Cn4-Cn5 119.7(13) 119.4(13) 119.3(13) 122.1(13)

Fn5-Cn5-Cn4 120.9(13) 120.1(13) 119.6(12) 118.8(12)

135

Table 36 - continued

n = 1 2 3

Fn6-Cn6-Cn5 115.7(10) 118.3(11) 117.6(10) 117.2(9)

Fn6-Cn6-Cnl 120.4(10) 118.8(10) 118.5(10) 119.7(9)

136

Table 37

Bond Distances and Bond Angles of Pentaf luorophenyl Groups

in C^{fph)^Co(cp) (tpp)

.

e

(a) Distances (A)

n = 1 2 3 4

Cnl-Cn2 1.387(14) 1.372(16) 1.394(14) 1.403(15)

Cn2-Cn3 1.388(19) 1.368(20) 1.398(19) 1.358(19)

Cn3-Cn4 1.387(17) 1.374(18) 1.370(18) 1.348(16)

Cn4-Cn5 1.382(17) 1.374(20) 1.372(18) 1.370(17)

Cn5-CnC 1.382(18) 1.363(13) 1.362(18) 1.384(17)

CnG-Cnl 1.385(14) 1.389(14) 1.408(15) 1.367(14)

Cn2-Fn2 1.322(11) 1.341(12) 1.339(13) 1.358(11)

Cn3-rn3 1.350(14) 1.338(17) 1.339(14) 1.338(14)

Cn4-Fn4 1.360(17) 1.339(19) 1.334(17) 1.335(16)

Cn5-Fn5 1.336(13) 1.354(13) 1.330(14) 1.361(13)

Cn6-Fn6 1.341(12) 1.355(13) 1.356(12) 1.348(12)

(b) Angles (°)

Cnl-Cn2-Cn3 122.4(11) 122.9(12) 123.4(11) 122.6(10)

Cn2-Cn3"Cn4 119.7(12) 119.2(13) 118.9(12) 120.5(12)

Cn3-Cn4-Cn5 119.6(12) 120.1(14) 120.2(13) 118.7(12)

Cn4-Cn5-Cn6 118.7(12) 119.0(12) 119.8(12) 120.4(11)

Cn5-Cn6-Cnl 123.9(11) 122.9(11) 123.8(11) 123.0(10)

Cn6-Cnl-Cn2 115.6(10) 116.0(10) 113.9(10) 114.5(10)

Cn -Cnl-Cn2 123.3(10) 123.8(10) 122.9(9) 124.2(9)

Cn -Cnl-Cn6 121.0(10) 120.2(10) 123.0(9) 121.3(9)

Fn2-Cn2-Cnl 121.4(10) 120.5(10) 119.1(10) 119.8(9)

Fn2-Cp2-Cn3 116.2(10) 116.6(11) 117.5(10) 117.7(10)

Fn3-Cn3-Cn3 120.4(11) 122,0(13) 119.9(11) 119.1(11)

Fn3-Cn3-Cn4 119.9(11) 118.8(13) 121.2(12) 120.4(11)

Fn4-Cn4-Cn3 120.0(12) 121.2(13) 118.9(12) 120.1(11)

Fn4-Cn4-Cn5 120.4(12) 113.7(13) 120.9(12) 121.2(11)

Fn5-Cn5-Cn4 119.7(11) 120.5(12) 119.9(12) 119.8(11)

Fn5-Cn5-Cn6 121.6(11) 120.5(12) 120.3(11) 119.8(10)

Table 37 - continued

n = 1 2 3

137

Fn5-Cn5-Cn6 119.4 (12) 119.3(12) 121.4(12) 119.8(11)

Fn6-Cn6-Cn5 117.7(11) 115.0(1.1) 117.6(11) 117.9(10)

Fn6-Cn6-Cnl 119.7(11) 119.9(10) 118.9(10) 120.1(10)

138

a

D4o

<4-l

UC•H

H ^^CO x:fo Cu

CO

<u or^ x:^ a.It) r-H

Eh >iC(U

J^

•Hu

O

Wat

enc<

COm'dc

en

oc(0

-p(A

a'dco

CO

0)

o

(04J

CO

•HD

(0

r--

Pi

vr>

O

x:

ou

^«

ou

11

fO

139

in in in

Ul CO CO

140

The fluorinated mctallocycles resist thermal decomposi-

tion better than the hydrocarbon analogs. ' Enhanced ther-

mal stabilities have been observed in other highly fluorina-

114ted metallocycles relative to their hydrocarbon analogs.

In the compounds of this study the triphenylphosphine ligand

and the four fph rings provide an effective shield for the two

double bonds in the metallocycles. Although the fluorine

atoms of the fph rings and the phenyl rings of the tpp were

omitted from Figure 10, the sterically hindered nature of the

metallocycle may easily be seen. The lack of a convenient

path for an attacking acetylene together v/ith the enhanced

thermal stability of the fluorinated derivatives may have

allowed the isolation of these intermediate metallocycles.

Metallocycles of cobalt and rhodium of the type presented

are reasonable intermediates in the catalyzed oligomerization

of acetylenes.

CHAPTER 7

CONCLUDING REMARKS

The structure of C^Co (H2dmg) (drag) (clan) shows the same

LIPS phenomenon as c£ Co (H^dtag) (dmg) (sulfa) /'^ These two com-

pounds exhibit the unusual feature of containing both neutral

and dianionic dimethylglyoxime groups. Also, the orientation

of the benzene ring of the sulfa and clan group in the respec-

tive compounds is over the dianionic dmg. The various dis-

tances and the relative orientation of the axial ligand in

both compounds suggest a n-type interaction. LIPS supports

the contention that "hydrophobic forces" are important in en-

zymic processes.^ The bis (diglyoxima to) cobalt (III) complexes

of aniline derivatives have here been shown to be useful mo-

dels for the examination of tliis type interaction. An exten-

sion of X-ray structural determinations to similar compounds

with other aniline derivatives and with other diglyoximes is

suggested. Low-temperature X-ray studies could effect better

resolution of the inter-drug bridge structure and the N-0

distances

.

An investigation of the fluorescence spectra of these

compounds could reveal additional information concerning the

interaction between the equatorial and axial ligands. The

fluorescence of 5-dimethylaminonaphthalene-l-sulfonamide was

observed to be enhanced while the fluorescence of carbonic

141

142

anhydrasG was diminished when a 1:1 complex of the tv/o was

formed. "* Although the major contribution to this observa-

tion is believed to be the ionization of the sulfonamide, a

portion of the change is attributed to a hydrophobic inter-

action.-''' ^^^ The fluorescence spectra of cobaloxime com-

plexes with aniline derivatives should help reveal tlie nature

of the interligand interaction as a function of the orienta-

tion angle.

The novel ligand dhphpy has been demonstrated as a bi-

nucleating ligand. The bridging site occupied by a chlorine

atom in [Ni2C£ (H2O) ^ (dhphpy) ] Cf^ clearly is accessible and

of convenient dimensions to accommodate a molecule such as

dinitrogen. Further development of this system as a possible

model for nitrogenase should include use of molybdenum salts

and work with the exclusion of oxygen. Synthesis of similar

ligands with saturated "side arms" is also suggested.

The compounds C^ (f ph) ^Co(cp) (tpp) and C^ (fph) ^Rh (cp) (tpp)

contain a butadiene fragment with each end bound to a metal

atom. The metal to carbon bonds are shorter than expected

for the single-bonded distance. The metallocycles are, there-

fore, believed to contain a delocalized Ti-bonding system.

While metallocycles should be higl;ly susceptible to nucleo-

philic attack and thermal decomposition the two compounds

studied here are very stable. The enhancement of thermal sta-

bility by the fluorinated substituents may be at least par-

tially responsible. Also, the presence of the four fph rings

143

along with the tpp and cp ligands provides a shield from

attack for the metallocycle.

The understanding of catalytic processes should improve

the efficiency of our existence. Hopefully, enzymic pro-

cesses occurring in nature can be duplicated in the labora-

tory by suitable models. These model enzyme systems may then

be applied to cure the diseased and feed the hungry.

APPENDIX ABOOTH ITl

A listing of the FORTRAN language computer program

BOOTHITl follows. This program was designed to interpolate

atomic positional parameters by Booth's method from the

values of a Fourier synthesis calculation. The Fourier syn-

thesis program v/ritten by Dr. Gus J. Palenik v;as modified to

store the calculated values on a magnetic disk. After supply-

ing BOOTHITl with input data of the approximate position of

each atom, the stored values are retrieved. The program esti-

mates the position of maximum electron density for each atom

from these Fourier synthesis values. The positional parame-

ters may be translated to equivalent positions and may be

passed to a bond distance and angle program. The resulting

fractional coordinates are punched into IBM cards in the for-

mat required for their input into the Fourier synthesis and

least-squares refinement programs.

144

145

»

146

147

148

149

n n

3

n3)

nna

rj

>z

V X

0^ r, -- -~ z c o•• j:— — •ULL <~

U. U. ID -C O D «» 0". OrjcG •-CI— i_

riiiz • _j< 2:

-•jjxl — OZ— II z

^hZ — — -AJ — M_

o

Xat-

z

+

> M

z z

+ +

-^ z z

og

^^je

I-

+

-> z z

•a 01

150

151

152

aoo

>2

in

>

»

JL'

>

J

0.z

L

+ -.

J

> II

I -

H c-< •

^ _l

> II

(.0

I •-

< •

> •

— u.

L. — - -^

*s '» ~ -< J + I

lj_ J. '^ J • '^ -»— »-^ *-4 9 ^.. »-* »-^

_J _' _l >-

» >

- _!

* •

in v,

a a

-. (\i

a a

_l

V)

u.

(/)

u.

a

II _j II -J

II >i II II

•X^ a.

- a7. J

z aza

153

iD

APPENDIX B

OBSERVED AND CALCULATED STRUCTURE FACTORS

Table B~l

Observed and Calculated Structure Factors for c£Co (H2dpg2)

-

(clan) •C2H^0H

15C

FCI rc FC FC f c FC I O FC

H=

157

FO FC FO FC ro FC

-1

158

1

23At)

6V

9 -10 -

1 1 -12 -

-li --12 --1 1 --10 --9 --8 --/ --C ~_ c. _-4 -

-1

H=

1

345t)

7es131 1

-1 1

- 10-y-t-7-C— c-

-4

H=

1 '1 1

l't31 'it

2H214J?0^2V<*i';31 'I -5

1 <i6

1 4C:

1 >*•-

1 ^.V1 tbI '.

1 '.0

1'.

1'. ol^fc147J '«a

1 i. t-

1 , K-

•137-l'»0-1 (

37031 3l'*9-143-143- 1 •'( S- WiB1'. C

- ) b:i- ic 1

-14 5-1 602oe300-139209-13ti

- j - 1 'j

-1 -

4 -

78-L-7-6-b-4

-1

H=

1 3d142

1 f V

2671'. 313S14414014b14614 7Ibl1'. a

2 1 y14 314fc1 1314630 4143

-1 bO- 1U.3-1 bl242

FC

106-bO-3-1

231e7

145•2PP

1 74129-190

4 2114-221 7 3-34-147

105-3

23 4166

-36 9-cn4 1 I

1

1

97125-SO-?7Clit*

-142-8933

-1 8-23ie3

- 132GO

277-2 27-36 3IC624-39-139-4?1 03

12

17497

-38

ie.97e

-143- 191

2019

- 126bb^7

-2 06-38

13

-4bC-6

157-16

4-4-3-2- 1

y-~

2t,

6O

101?141 618

-20-1»^-16-14-1 2-10-8-6-4

1

234b6789

101 1

la131 'I

15161 7

If19

-19-IP-17-16-15-14-13-12-1 1

-10-9-8-7-6-5-4-3-2-1

FO

- 1 4 92 3 4

- 14 «-lb)-14b

b9 2^^?113 1

189/51 7247-) 624 6

-13756.

i

4cit>- I 4 3-136bb7

b44 -i 4

3724 6'91.

6

1 1 2 6

rc

- 13884

-29-bO-79

569-9161113

- 1823lt97- 7 / 2

7 2125

- ^6046 I

- 1 3 1

-156565

-626£39

-46 3-3/8444

-Sb710/3

K-

314- 1 001 529209

I 2 55- 1 1 ;.

3063i;7359

-11438 24 1 742 633650 '•l

- 1 3 •

-13 9-13-.-136-146-1 3H3502<'024 I

24 5-13^-12 J33

- 1 1 362 358 1

138 560238 4

1273180bi.'8

-98

309- 1 53

- 1525-2311271-58

-258380

-3222

373-4 14-43534 6555

- 161-340

38-4 1

89-55

-373170235

-22 5121-j'2

-29229

6 19-583-1377

£91399

-123978

-491-272

29

C78<i

101 1

121314lb1617le19

- 19- le-: 7-16- 15-14- 1 3- 12-1 1

-10-9-8-7-6-5-4-3-2-1

f C

232i03? 79-111lie2C4£231512 to-13013 529 /

2ca- I .* 4-14 5197

-14 1

-13542 5i9fc::3:i

2 54; 14365-116-1122002 04IC75-112-114-113S.CS631

f C

213tl C

-:: 12-9 s.

It2- 3 1

-ibC-7 1

-22 t-7914 1

237-248-17-.

64-fc I

198-1 8

-4C33 :.4

424-312 64383251C9

- 148ICO

-1 05o-25 1

-73-1 93t7267 1

K-

2. K-

159

FO FC FO FC FO FC FO FC

160

to FC f-0 FC rc FC FO FC

1 7 -

161

L

162

L

163

L

164

FO FC FU r c FC FC FO FC

1 1

165

L

166

FCl FC FO FC 10 fC FO FC

s

167

FO FC FO FC FO FC FO FC

1 z

168

rv re FC »-c f c f c ru FC

v

169

L

170

r u re KU FC » O FC f O FC

-13

171

FC PC FO rc FC FC FO FC

-2

Table B-2

Observed and Calculated Structure Factors for [Co(Hdnig)2-

(clan)2]c£

173

FO FC FO f C FO rc FO FC

174

FO FC FO fC ro rc i (I rc

175

FO rc FO f-C FO FC ro FC

-4

176

L

177

FO rc FO FC r o f-c ro FC

2

178

ru FC FO FC HO FC f O FC

», «,

379

L

Table B-3Observed and Calculated Structure Factors for H^dhphpy (NO^)

^

181

n=

ee

10

h--

6e

10

2.46e

10

1-:=

C?.

A6e

10

H=

p.

6

H=

H-

PO

0, K

32 1

1 01;

>: 9 2

37

2, K =

PA 7

269f.73

FC

3?3- !C0?63

-?ft2

-?'i 1

?????

77

K-

C

ee

6

3M130?6

1C.99

6,

b3113 1

-J 8SB

-22

e. K

296;.-

<5u3&0AC

- :?q7

3i".- I r:.c.

sets

i;=

10: K =

b't

2 3?/j4 2396 Abe -2 i

096P

-- 239 C

1 A . i:

-1 a-1 922?79

r.-';0

i;251 26- 30

14

-r9y

f-3^3

-41

3?5??9-*. 510

?3- 4 C2-5A

I

233-e?

16, K =

2

2

I Oh-2 1

-21

IP. K =

It.Vbl

-22

- 1 ^2

-16 3

2

FO

20. K:

32«22

FC

2085

-21?, K=

<IV0

-20,

2

182

f D rc f o PC FC rc (a f c

7

183

H=

H=

H=

H=

1

234

FCI

G. K-

FC FO PC FO FC

1

184

A5

7

BV10

FO

407H73 'J

-2097

FC

ACA

3C)

-?0

90

H= K =

i

23

t)

678910

36133?1 L.t.

!<' 1

J (. t.

1 I''

3e79

-20-2040

3'.)5320166

- I 17It?1 1 ?-307 'J

?1A9

K =

1

234b6789

1 19429

t>ti

1 AO703 A23331513C.

1124 2 '3

67- 1 40

7 6-16-2A0-23-48-32

H= K =

1

2346b7e9

H=

1

234567e

l6Ci79102m11757b3124-2 I

48

O. K

bAO2i>'>- 16122-

I e134583094

4bC7

1

234

r o

-21-20-2162

10lb-B-53

14, K =

10261

1 1 1

63-21-21-22

91-61

-107- Ol-7-2

-10

4b678910

y-

1

?34

H-

1

23

H^

H=

16, K-

-2 1

-21-2 1

-2168

18, K.=

-21-2)

'i

-23

2 .'---

-23

-2 0. <=

-170-01

-103-0012156

-43- 129

20-51

1

2345

461 1 1

162-2342

-337

-21-1771

I I

-44320

-1 1

23no161

36

H= - 1 tj ,«.=

3456769

10

FO

_lo3013213'.

282225

/ 1

-214 3

-10. »-

2 66113752 1

eo-2062£21-21-22

10-40

- 12914229423 669-2

-30

-263-16-*-6610

-e42066

-2192820

1

2

4567e910

-8. K =

3710763

-I 7C2165652751.1748

--361C9-^•6-2659171-7 7

-2V6-125-49

H= -e, K--

536-253

-5- u e

10141-532599

34567

33-22-22240-224646

H= -16.

H= »0^ K =

1

2345678

-21336 82032566 335-23

-401817

-2401 1

4354

2239

-68-209-26 1

-5C-3812

67e910

42 1

1732J;3- 16e2

-li.^4056

-22141

1

2345678910

FO

1 12165k 1052

i!08212101-2066

-21

FC

106lb 7

llO51

206-209-94-460- 1

H = K-

H=

1

2345678910

202661275303 1

5553125-21169

1

2345678

I 45U>1- 1 t,

- 19- 194864

-2 I

36

1 46174

2-1

1

33-69-330

H= -2

H- - 1 4 K.=

H= I? K-

1

234567e9

32-191 10-20-21299425244

1

23

2 734

17 1

54

-1631

- 17355

H= •12

3t>

377

1 1'>

-2-17304-49-57-47

4

27

1

2345678910

112- 152^46244

-184 2626836

1

234567

9

5079

2AU1 CO2 6022565

-19-20-21

H=

412-1692A510

-90-345

-59-2813'.

-201-66 527729

-2758

-92-126

25171

-11338

-24163

-4 2

47-59-9041

1

234567e9

5646

-161677289399858

50-6624 398

2r.7-226

681416

1

47-63

6167-74-8929975744

H- K--

1

234c

67

8

123404 65341567197

-21

125-38-4056

-42-6 1

-6498

-21

F = K =

1

345678

53233169-194771

-2166

44-235-165

-47-721562

-1 1

11 K =

1

234

567

1 615731

-20-202,7

31-21

165155-27lA

-13-36-626

h= 13. K =

1 , K= 5

149 -138

I

23

-20877987

28-867391

185

456

1

23A5

FO

1 1 '.

-21-2 1

H=

1

23

H=

1

J5,

37-? I

1 1 46^1

-22-22

IV, K

-21-22-21'>3

1^. K

-23-22

K =

H= -19,

1

23A5

371311H3-2?'23

FC

1 151

107

i-g

1

-31-?552

5

30-V

-211 19-179

9?0

FO FC

-17,

1

186

ro re

H=

1

187

FO FC FO FC FO FC FO FC

2

188

H=

M =

1

Table B-4jlated Stri.

(dhphpy) ]Cl^'2E^0Observed and Calculated Structure Factors for [Ni,c€ (H„0) .-

2 2 4

190

L

191

FO FC FU FC FO FC FU FC

-7

192

FO FC FC FO FC FO FC

10

193

FO FC FO FC FO FC FO FC

-13

194

FO FC FO ^C FO rc FO FC

24

195

FO PC FU FC FO FC FO FC

-Ifi

196

FO FC FO rc FO FC FO FC

20272b?b2 4232221

197

FO FC FO FC FO FC FO FC

198

L

199

L

200

— 1>

-A-J

1

M-

t

o4-

34567d9101 1

1314

-2 6-.?0-ii4-23-22-21-20-\<^-Hi-1 /

- 16-15-i 4-13-12-1 1

-10-9-8-7-6-5-4-3-2-1

FO

331423 -

24«200211

7, K =

b30-tu701-811C9-80283443-81-80233-82-832i.6-8012921 84811062314 703822191281 1828'^228Ibl-80143224428225b3 73 727086173771 847 77-80

FC

-3484 08-7 38-243197-222

-62 51 6

-88?t.8

1 8 939

2 9 4-4-j>0

84-24

-2 4 4-72

622733

-812354 99-148215

-'4 5 3-397227153-52? 8 '»

21 91 8 2-931 172124 3 7

- 1 'VI- 5 4 4-<i 5-710814383150730-17

K-

1

Z345678910

-?b-24-23-22-21-20- 19-18-17-16-15-1 4-13-12

9, K=

666-60-811 15327348-832 192 84235135169-6432 84 77233-8132313022 1

-79-80-803 62-31

-602-8

1 1 I

12.9342

-3'*2-66

-21 o-274

1 9 1

1 38-127

35-325-49323088

351105

-2531 0181b

-3^fj26

1

1

10-9-8-7-6-0-4-3-2-I

F O

236-8 1

3731 3237329346597-82-8 I

-8 1

1 1

1

234

-23-22-21-20-19-

I 8-17- lo-Id- 14- 13-12-

1 I

- 10-9-8-7-o-5-4-3-2-I

r1 =

- 18-1 7

-1 6- 15- 14- 13-12- 1 1

-10-9-8-7-6-5-4

r| =

1 74-84^^"^-at-87-842394ol«4 2 5-82-81-3 1

350I 5 9209-30-79ir-2,'5 7

1 <\ 7246330

2361 1 91 253o4

1

234567a9101 1

121 314

FC

-244-57

-1203'-> J26432159 764

- 149 7

1 41-60341-95-3332

-3014 654o2-51Z717

-344- 155-225-42

6- 150-2o0

1 1 3225317

- I 1 5~7 )

-3f.8-7

13, K-

-85-87-8o190-85146-851 5o-8524 6-87-87-38-8?420

K =

1132732-724 I 5821 5a44233538 41 * I

5 2 U30 aI d 9,^^Z1 1 /

- TO1 22-72

-1 73-301 54209759

211 20-45-94

- 1 35-4 Oo

10

-11967 75-1

3 95823

-15 1

-44 3- M-o-334- 1 t^d

5 3t>

3"/c-1 Ou22 3-y3

15lu1 7IQ1920212 2

H-

1

23456789

101 1

121 31415161 718192

-2 3

-2 I

-20-19- lb-17-lo-15-14-1.3-12-1 I

-10-9-8-7-6-5- 4-3-2- 1

FO

171-8136^;18248 I

-33-842 33

2, K::

-7222040274432621 9317-79-784922iJ4563 79-62204<; 7 J-3 2454218-304') 61 5534122644 I

1 65158428-8155 52 56-784904 84438640l<>61 4 55613222 557 5 3377302

H:

FC

1 71I 02

-37 8-190-4 30-2022

-24 6

1

8121 441

-7 513.51

-I 6 9

90-3

4 72321442

-33347

- 21 3-4 33

-437233103

-4521 3 6

- 3 4 92024'»321 1

-212-'»34

o-606262

- 95034 9 J

-4 39639

-1911 46DOO

-34 9-253-760-3 9 1

3 J9

K-

1

23456739

101 1

1 213141 51 61 7•2a-23

695461344435538-7926141 43953D140027 7-ill2571311295-0421 8233422

10

71 9-473

-397-51 1

522504 334012 93

-4 02-283-I 09-250

1 58-276

1 I

200-2334 19

-22-21-dO-I 9-1 8-

I 7- 16-

I 5- 14-13-12-

I 1

- 10-9-8-7-6-5-•-3-2- I

H-

FO

2.4 3200-825'yO-8065199-802 40361334471653-77- 7b20 42-.>3

-7501 6-752 1 7539

H =

K =

201

FO FC FO FC = o FC FO = C

1

1

202

FO FC Fl) FC F O FC FO FC

1 1

203

FO FC FO FC FO FC FO FC

-3

Table B-5

Observed and Calculated Structure Factors for C^ (fph) ^Rh (cp) (tpp)

205

FO FC

H= K=

1

Jr

3456789101 1

121314151617

-211C9767 1

21 3<tCB33412A7t.317iy361-bO3^2!<4&3S21432 5138

1 OP1630-f*?2_

Io ^

- 21 1

-1 240

73 334439

-7.<>o-17253 6234

— ^ <*"^

-173

K-

1

23456769IC1 1

1213141516

-18-17-16-15-14-13-12- 1 1

-10-9-8-7-6-5-4-3-2-I

164 415530 1

1 179332

I 2a912853 73&925441-634271202S2— ^, *!

22 5-C7153192-6 93:) 3-53432123t2033125763 1

308S"J9IC250d1102552

1

-2456-Bl

-- 1 5 41 cr4-259

- 1 r63-loe51 9423

-?48-423-6403134

-2G31

237-917 4107-90

-375-524 '5134

-84 2-304250CO 7235

-91 5-36553

I 44 9-G50

K =

1

2

456789101 1

1?131415-19

7974 4't

61 1

12«t3157

114 7

7 73-^83e.a24 3329-66323-6/301-70104

195-363-772-1260223

1 1C714

-37 5-3442523 34-30

-3173 6

30 1

3886

1817-IC15I 4-1 3-12-! 1

-10-9-r>-7-6-5-4-3-2- 1

FO

177-65190187172-616175^ 1

4 6031352 21415-b^1607353-459201C6

FC

17322

-191183157-6

-62 1

-50 4453299

-53714 9 3-53162942V18'-'

-518154

K=

1

23456789

101 1

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— 5

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114. S. A. Gardner, H. B. Gordon, and M. D. Rausch, J. Organo-metal. Chem., 60, 179 (1973).

115. J. Olander, S. F. Bosen, and E. T. Kaiser, J. Am. Che^i.

Soc. , 9_5, 1616 (1973) .

116. A. D. Booth, "Fourier Techniques in X-Ray OrganicStructure Analysis," Univ. Press, Cambridge, England,1948, p 64.

BIOGRAPHICAL SKETCH

Douglas Allen Sullivan was born November 9, 1945, in

Huntington, West Virginia. In May, 1963, he was graduated

from Vinson High School, Huntington, West Virginia. He

received the. degree of Bachelor of Science in Chemistry from

Marshall University in May, 1967. After studying at the

University of Florida from September, 1967, to August, 1968,

Mr. Sullivan taught chemistry, physics, physical science,

and mathematics for the Wayne County (West Virginia) Board

of Education. He then returned to the University of Florida

in September, 1972, and received a Master of Science in

Teaching degree majoring in chemistry in December, 1974. He

is a men\ber of the American Chemical Society. Mr. Sullivan

is married to the former Jeanie Delaine Puckett of Titusville,

Florida. They have a three-year-old son, David 0' Donald

Sullivan.

237

I certify that I have read this study and that in myopinion it conforms to acceptable standards of scholarlypresentation and is fully adequate, in scope and quality,as a dissertation for the degree of Doctor of Philosophy.

Gus J. Palenik, ChairmanProfessor of Chemistry

I certify that I have read this study and that in myopinion it conforms to acceptable standards of scholarlypresentation and is fully adequate, in scope and quality,as a dissertation for the degree of Doctor of Philosophy.

'^^^C^/i-L^

R. Carl StouferAssociate Professor d\

Chemistry

I certify that I have read this study and that in myopinion it conforms to acceptable standards of scholarlypresentation and is fully adequate, in scope and quality,as a dissertation for the degree of Doctor of Philosophy.

George E. ^yschkewitschProfessor of Chemistry

I certify that I have read this study and that in myopinion it conforms to acceptable standards of scholarlypresentation and is fully adequate, in scope and quality,as a dissertation for the degree of Doctor of Philosophy.

John F. Helling (^Associate Professor of

Chemistry

I certify that I have read this study and that in myopinion it conforms to acceptable standards of scholarlypresentation and is fully adequate, in scope and quality,as a dissertation for the degree of Doctor of Philosophy.

Richard R. RennerProfessor of Education

This dissertation was submitted to the Graduate Faculty ofthe Department of Chemistry in the College of Arts andSciences and to the Graduate Council, and was was acceptedas partial fulfillment of the requirements for the degreeof Doctor of Philosophy.

December, 197 5

Dean, Graduate School

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