Z E I T S C H R I F T FÜR N A T U R F O R S C H U N G

T E I L Β V

Anorganische Chemie/ Organische Chemie

Kuratorium

E . B Ü N N I N G , Tübingen A. B T J T E N A N D T , München M. E I G E N , Göttingen W . G E N T N E R , Heidelberg

Schriftführende Herausgeber

Η. P . F R I T Z , München R . G O M P P E R , München H . S C H M I D B A U R , München

Beratende Herausgeber

E . 0 . F I S C H E R , München G . G L I E M A N N , Regensburg H . N Ö T H , München D . S C H U L T E - F R O H L I N D E , Mülheim/R. F . F . S E E L I G , Tübingen W . S T E G L T C H , Bonn W . V O E L T E R , Tübingen A . W E I S S , München

0m

H E R A U S G E G E B E N U N T E R M I T W I R K U N G

D E R I N S T I T U T E D E R M A X - P L A N C K - G E S E L L S C H A F T

B A N D 36b H E F T 1 J A N U A R 1981

V E R L A G D E R Z E I T S C H R I F T F Ü R N A T U R F O R S C H U N G T Ü B I N G E N

Contents Ζ. Naturforsch. Vol. 36b, No. 1, January 1981

Original Communications

Electrochemical Syntheses, I V . Metal Carbonyl Compounds of the Iron Group Elements ( I n German) J . G R O B E and B . H . S C H N E I D E R 1

Electrochemical Syntheses, V . Phosphane Substi­tuted Metal Carbonyls of the Iron Group Elements ( I n German) J , G R O B E and Β. H . S C H N E I D E R 8

The Crystal Structures of BaSe2 and BaSe3 F . H U L L I G E R and T . S I E G R I S T 14

Acyl - and Alkylidenephosphines, X V . 2,2-Dimethyl-propyHdynephosphine, a Stable Compound with a Phosphorus Atom of Coordination Number 1 ( I n German) G . B E C K E R , G . G R E S S E R , and W . U H L 16

I R , s iP, 5 5 M n and 1 8 6 » 1 8 7 Re N M R Spectroscopic Investigations of Some Carbonylmanganese and -rhenium Complexes ( In German) A . K E ? E C I and D . R E H D E R 20

On Oxidpnictides: Preparation and Crystal Struc­ture of Ba2Mn 2Sb20 and Ba2Mn2Bi20 ( I n German) E . B R E C H T E L , G . C O R D I E R , and H . S C H Ä F E R 27

Solutions of Li thium Tetrahydrido Aluminates in E t h e r s : a 7 L i and 2 7A1 N M R Study H . N Ö T H , R . R U R L Ä N D E R , and P. W O L F G A R D T 3 1

Penta-Coordinated Complexes of Bis(2,4-pentane-dionato) Copper(II) with Some Oxygen Donor Organic Solvents B . P . B A R A N W A L , G. K . P A R A S H A R , and R . C. M E H R O T R A 42

The Reaction between Borontrifluoride and Sodium Diethylphosphite Synthesis and Reactions of Tris(diethylphosphitoborane) ( In German) H . B I N D E R and J . P A L M T A G 45

Perfluoromethyl Element Ligands, X X I V ; Organotin Compounds as Reagents, I I I . Cleavage Reactions of the Element-Element-Bond in Compounds of

the Type R n E - E R m (R = CH3CF3; Ε = P , As , S , Se, T e ; n,m = 1, 2 ) ( In German) P . D E H N E R T , J . G R O B E , and Duo L E V A N 48

Preparation and Crystal Structure of SbCl8-l2*l ,4-Dithiane ( In German) G . K I E L 55

Mössbauer Spectroscopic Studies of Monosubsti-tuted Pentacyano Ferrate(II) Complexes, N a 3 [ F e ( C N ) 5 R N H 2 ] · n H 2 0 A. N . G A R G and P . N . S H U K L A 59

Preparation and Spectroscopical Characterisation of Tetrakis(chloro-iodo)oxalato-osmates(IV) ( In German) W . P R E E T Z and H . S C H U L Z 6 2

Preparation and Characterization of Monoorgano-bismuth(III) and Bismuth(III ) Derivatives of Mercaptocarbonic Acids ( In German) U . P R A E C K E L and F . H U B E R 70

Collisional Activation Mass Spectra of CeHeM* and C 7 H ? M + Fragment Ions from Transition Metal π-Complexes ( In German) J . M Ü L L E R and F . L Ü D E M A N N 74

Crystal and Molecular Structure of (Tetramethyl-cyclobutadiene)c£s-1,2-dicyano-ethene-1,2-dithiolato-nickel(II) ( In German) R . H E M M E R , Η. A . B R U N E , and U . T H E W A L T 78

Some New 1-D Compounds with Metal-Halide Chain D . L A Y E K and G. C. P A P A V A S S I L I O U 83

Non Deprotonated Metal Complexes of the Bis -amide Tetradentate Ligand N,N'-(Dipicolyl)- l ,8-naphthylenediamine T H . F . Z A F I R O P O U L O S , S. P . P E R L E P E S , P . V . I O A N N O U , J . M. T S A N G A R I S , and A . G . G A L I N O S 87

Metal-π Complexes of Benzene Derivatives, X I I I . Bis(methylthio-?y-benzene)chromium(0). Prepara­tion and Function as a Bidentate Chelating Ligand ( In German) H . B U R D O R F and C H R . E L S C H E N B R O I C H 94

Continued overleaf

Stabilization of a Host-Guest Type Complex by Bifurcated Hydrogen Bonds: 18-crown-6 · (2,4-Dinitrophenylhydrazine) R . B J L G E N F E L D and W . S A E N G E R 242

Activation of Steroid Systems to Alkylating Agents ( In German) M . W I L E : and K . S C H M I T T 248

A New Route to lH-Pyrido[l,2-a]quinazolines F . S . G . S O L T M A N , W . S T A D L B A U E R , and T H . K A P P E 252

Synthesis of Kaempferol-3-0-(3 / ' ,4 ' ' -di-O-a-L-rhamnopyranosyl)-/^D-galactopyranoside and its Comparison with the Natural Ascaside Isolated from Astragalus caucasicus I . R I E S S - M A U R E R , H . W A G N E R , and A. L I P T 1 K 2 5 7

Isosilychristin, a New FlavonoHgnan from Silybum marianum L . Gaertn. ( In German) M . K A L O G A 262

Notes

Contributions to the Chemistry of Phosphorus, 89. Cyclization of a l,3-Dihalogen-l,2,3-triorganyl-triphosphane to the Corresponding Triorganyl-cyclotriphosphane ( In German) M . B A U D L E R and J . H E L L M A N N 266

Preparation of Antimony(V)tetrafluoridepenta-fluorotellurate(VI), S b F 4 O T e F 5 and Antimony-(V)trifluoride-bis[pentafluorotellurate(VI)], S b F 3 ( O T e F 5 ) 2 ( In German) 0 . L E I T Z K E and F . S L A D K Y 2 6 8

A New Preparative Method for Cesiumhydroxide ( I n German) H . J A C O B S and B . H A R B R E C H T 2 7 0

Redox Properties of Platinum Uraci l " B l u e s " : A New Type of Paramagnetic Species M. S E U L , H . N E U B A C H E R , and W . L O H M A N N 2 7 2

High Pressure Reactions, X I I I . Synthesis of (—) Cannabidiol at High Pressure ( I n German) H . - J . K U R T H , D . ΒΓΕΝΙΕΚ, and F . K O R T E 2 7 5

Isolation of a New Natural Quinone, 2 -Hydroxy-6-methoxy-3,5-dimethyl-1,4-benzoquinone, from the Potato Culture Solation of Phoma tmsaJbiae Yokogi O. S O G A and H . I W A M O T O 2 7 7

Sulfonamidyls, 4 . Ab Initio MO Calculations on Sulfonyl and Carbonyl Substituted Aminyl Radicals H . T E E N I N G A , W . C. N I E U W P O O R T , and J . B . F . NT. E N G B E R T S 2 7 9

E r r a t u m 2 8 2

I S S N 0340-5087

Contents Ζ. Naturforsch. Vol. 36b, No. 2, February 1981

Original Communications

Synthesis of Sodium-Chelates of Methylen-bis-iminodiphenylphosphorane] ( I n German) R . A P P E L and K . W A I D 127

Synthesis of Symmetrical Diaminoearbodiphos-phoranes R 2 N P h 2 P = C = P P h 2 N R 2 ( I n German) R . A P P E L and K . W A I D 131

T h e Crystal Structure of Methyltriphenylphos-phonium Hexachlorotitanate ( I n German) E . H E Y and U . M Ü L L E R 135

Preparation and Characterization of Tetrabutyl -ammonium Tetraiodooxotechnetate(V), ( T B A ) [ T c O I 4 ] ( I n German) G . P E T E R S and W . P R E E T Z 138

Reactions of ThaJBum(III ) Carboxylates with Ketones ( In German) M . V O L L M E R H A F S and F . SUBER 141

CyeMc Diazastannylenes, X . The Crystal and Mole­cular Structure of a Molecule with a Distorted Cube-Shaped SnaNeO-Cage ( I n German) M. V E I T H and 0 . R E C K T E N W A L D 144

O n the Reaction of Aromatic Phosphane Deriva­tives with Electrons, I . ( I n German) W . K A I M 150

Diazaborolidyl - a Stable Substituent at Sulfur Nitrogen Compounds ( I n German) W . H A U B O L D , H . G . F E H L I N G E R , and G . F R E Y 157

- Structures and Vibrational Spectra of Tetramethyl­ammonium α-Dodecatungstosilicate and Tetra-butylammonium /?-Dodecatungstosilicate ( I n German) J . F U C H S , Α. T H I E L E , and R . P A L M 161

Synthesis and Structure of 1,2,3-Thiadiazol- and 1,2,3-Selenadiazol-Pentacarbonyl Complexes of the Elements Chromium and Tungsten ( I n German) V . B A T Z E L and R . B O E S E 172

O n Cyanohalogenomercurates of Alkali Metals ( I n German) G . T H C B L E , Κ. B R O D E R S E N , and H . F R O H R I N G 180

Metallomethanes, I V . Molecular and Crystal Struc­ture of Bis(chloromercuri)methane CH2(HgCl)2 ( In German) K . - P . J E N S E N , D . K . B R E I T I N G E R , and W . K R E S S

188

P t ( I I ) , P d ( I I ) and C u ( I I ) Complexes with the Ligand 4,4,5,5-TetramethylimidazoHne-1-oxyl-2-m-pyridyl-3-oxide ( In German) Κ. E . S C H W A R Z H A N S and A . S T U E F E R 195

Transition Metal Sulfur Ylide Complexes, X L Structure and Reactivity of ?? 5-Thiacyclohexa-dienyl-l-oxide Complexes of Chromium (In German) L . W E B E R , D , V E H R E S C H I L D - Y Z E R M A N N , C. K R Ö ­G E R , and G . W O L M E R S H A U S E R 198

Transition Metal Complexes of Diazenes, X V I . Structure and Mössbauer Data of (2,3-Diaza-noTbornene)¥e3(CO)d ( In German) H . K I S C H , C. K R Ü G E R , and Α. T R A U T W E I N 205

Electret Model for the Collective Behaviour of Biological Systems H . B I L Z , H . B Ü T T N E R , and H . F R Ö H L I C H 208

The Metal Complexes of Heterocyclic ß-Diketones and their Derivatives, Part V I I I . Synthesis, Structure, Proton N M R and Infrared Spectral Studies of the Complexes of A l ( I I I ) , F e ( I I I ) , C o ( I I I ) , R h ( I I I ) , I n ( I I I ) , and Z r ( I V ) with 1 -Phenyl-3-methyl-4-trifluoroacetyl-pyrazolone-5 ( H P M T F P ) E . C H . O K A F O R 213

(Aminoethynyl)metallations, I X . Reactions of Y n -amines with Cyanoketenes ( In German) G. H I M B E R T and L . H E N N 218

Preparation of 1,3-Dimethyl-6-hydroxy-dihydro-thymine by Photochemical Addition of Water to I , 3-Dimethyl-thymine ( In German) E . F A H R and P . F E C H E R 226

Kinetic Studies of the Methanolysis Reaction of Chloromethylated Phenols ( In German) G . S T E I N , V . B Ö H M E R , W . L Ö T Z , and Η . K A M ­M E R E R 231

Continued overlefg

F i r s t L iquid Crystal Azulene Derivatives (In German) K . P R A E F C K E and D . S C H M I D T 3 7 5

Sesquiterpene Esters of Type Β from Euonymm europaeus L . ( In German) A. R Ö M E R , Ή . T H O M A S , B . K R E U E L S , and H . B U D Z I K I E W I C Z 3 7 9

7H-Imidazo[ l ,2 -a] - and -[l,5-a]azepine-7-ones (In German) U . W O L F 3 8 3

Electrochemical Properties of Pyridine and D i -hydropyridine Derivatives (In German) G. A B O U - E L E N I E N , J . R I E S E R , N . I S M A I L , and K . W A L L E N F E L S 3 8 6

K i n e t i c Investigation on the Hydrogen Transfer from Dihydropyridines to Hydrazyls ( In German) G . A B O U - E L E N I E N , J . R I E S E R , N . I S M A I L , and K . W A L L E N F E L S 3 9 1

Notes A Method for the Preparation of Anhydrous

R u t h e n i u m ( V I I I ) Oxide ( I n German) R . L Ö S S B E R G and U . M Ü L L E R 3 9 5

Photoproduction of Hydrogen from Water Catalysed by Metal Sulfur Chelates R . B A T T A G L I A , R . H E N N I N G , and H . K I S C H 3 9 6

i»C, m Spin-Spin Coupling Constants, V I I L 2-Methyl- and 3,5-Dimethyladamantane ( I n German) R . A Y D I N and H . G Ü N T H E R 3 9 8

A Spin T r a p Investigation of Azolyl Radicals V . Ν . B A B I N , V . V . G U M E N Y U K , S. P . S O L O D O V N I -K O V , and Y u . A . B E L O U S O V 400

Methoxymercuration-Demercuration of Pheromo-nes for Double B o n d Position Determination ( I n German) 0 . V O S T R O W S K Y and K . M I C H A E L I S 402

I S S N 0340-5087

Contents Ζ. Naturforsch. Vol. 36b, No. 3, March 1981

Original Communications

Interhalogen Cations: Preparation and Crystal Structures (143 Κ) of I 3 Cl 2 SbCle , I3CI2AICI4 and I s B ^ S b C l e ( In German) S . P O H L and W . S A A K 283

Synthesis and Crystal Structure of Bis(N-methyl-hydroxylainido(l-)-0,N)(N-methyl-N-oxo-aUthio-carbamato-0,S)-oxo-molybdenum(VI) ( I n German) W . H O L Z B A C H , K . W I B G H A B D T , and J . W E I S S 289

S4N4 and its Derivatives: Molecular and Crystal Structure of S e N 4

2 + ( F e C l 4 - ) 2 ( In German) U . T H B W A L T and M. B U R G E R 293

Synthesis and Stabilization of (Benzoyl- and Penta-ftuorobemoyloxy)diphenylphosphane and Com­parison with the Corresponding Isomeric Aroyh diphenylphosphane Oxides ( In German) E . L I N D N E R and J . 0. W U H R M A N N 297

Electrochemical Syntheses, V I . Electrochemical Substitution of VIB-Hexacarbonyls M(CO)e

J . G R O B E and S . Z I M M E R M A N N 301

Alkoxohalogenotellurates(IV): Preparation and Structure of Tetraphenylphosphonium Trichloro-(dioxo-ethylene-COOteUurategV) ( In German) K . B Ü S C H E R , S. H E U E R , and B . K R E B S 307

Opening of the B10H102" Cage to Give B10H14 Ή . M O N G E O T and H . R . A T C H E K Z A I 313

(?73-Benzyl) (^-cyclooctadienejrhodium (I) Com­plexes ( I n German) H. -O . S T Ü H L E R and J . P I C K A R D T 315

Synthesis and Properties of B i - , T r i - and Tetra-nuclear Transition Metal Complexes with the OrganometaUic Chelate Ligands [C 5 H 5 M{P(OMe)20}2] e (M = Ni , Pd) ( In German) H . W E R N E R , T . N G O - K H A C , C. F R I E B E L , P . K Ö H ­L E R , and D . R E I N E N 322

1 2 6 T e N M R Shifts and T e - P CoupUng Constants of Phosphane Tellurides, Tellurophosphanes, and Tellurophosphane Complexes ( I n German) W . - W . DTJ M O N T and H . - J . K R O T H 332

On the Reaction of [(CO)4FeC(0)NMe 2]-[C(NMe2J3 +

with Some Diorganoboron Bromides ( In German) W . P E T Z 335

Enehydrazines, X X X . Phenylogous Enehydraziixes without a Direct Ν,Ν-Bond ( In German) W . S U C K O W and W . T U R N S C H E K 339

Thermolysis of 2,2-Dihydro-l,4,2-oxazaphosphol-4-enes, I . Dimerization of Bis(trifluoromethyl) Substituted Nitrile Yhdes ( In German) Κ . B Ü R G E R , Η . G O T H , K . E I N H E L M O , and A . G I E R E N 345

Thermolysis of 2,2-Dihydro-l,4,2-oxazaphosphol-4-enes, I I A Simple Synthesis for Fluorine Sub­stituted N-Vinyhmidoyl Chlorides ( In German) K . B U R G E R , H . G O T H , and E . B U R G I S 353

Kinetics of Oxidation of Tryptophan by Sodium Hypochlorite T H . R A U S C H , F . H O F M A N N , and W . H I L G E N ­B E R G 359

1,4-Cycloaddition of p-Benzoquinone; 1 ^-Naphtho­quinone and N-Phenylmaleimide to 9- Vinylidene-xanthene (or Thioxanthene) Derivatives S. B . A W A D , A . B . S A K L A , N . F . A B D U L - M A L I K , a n d N . I . S A M A A N 362

Reactions of Amino Acids on 2-Methylmercapto-hydantoin Derivatives. Synthesis of Imidazo-imidazoline and Imidazoquinazohne Deriva­tives H . A . D A B O U N , A . M. A B D - E L F A T T A H , Μ . M. H U S S E I N , and A . F . A . S H A L A B Y 366

A Fundamental Study of Quantitative Desulfuriza-tion of Sulfur Containing Amino Acids by Raney Nickel and its Character S H . O H M O R I , K . T A K A H A S H I , M. I K E D A , and T . U B U K A 370

Continued overleaf

Photoditneris^tion of - 6-iratts-Styryl-4-methoxy-2-ρντοη,θ; (== 5,ß-Dehydrokawain) (In German) . M. K A L O G A and I . C H R I S T I A N S E N 505

Contributions to the Synthesis of Cystine Peptides Illustrated by the Total Synthesis of H u m a n Insulin ( I n German)

Β. Κ A M B E R 508

Notes New Phospha(III)azenes ( In German)

0 . J . S O H E R E R and H . C O N R A D 515

Reaction of (η3-AUylX^-cyclopentadienyl) Palladium with 2,3-Bis(diphenylphosphino)-maleic Anhydride ( In German) D . F E N S K E and A . C H R I S T I D I S 5 1 8

Tl4Ge4Seio, a Thallium(I) Selenogermanate with the Adamantane-Iike Anion [Ge^eio ] 4 " ( In German) G . E U L E N B E R G E R 521

Isolation of Dihydrokaempferol from Silybum marianum L . Gaertn. ( In German) M. K A L O G A 524

I S S N 0340-5087

Contents Ζ. Naturforsch. Vol. 36b, No. 4, April 1981

Original Communications

The Crystal Structure of TeeOnCfe (In German) W . A B B I E L 4 0 5

On Bariumthioantimonate(III) BasSbeSi7 ( I n German) W . D Ö R R S C H E I D T and H . S C H Ä F E R 4 1 0

Zintl Phases with Binary Anions: BaGe2P2 and BaGe2ÄS2 ( In German) Β E I S E N M A N N and Η . S C H A F E R 4 1 5

U V Photoelectron Spectra of Some Bent Bis -(77 s -cyclopentadienyl)NiobiumandTantalum Com­plexes H . V A N D A M , A . T E R P S T R A , A . O S K A M , and J . H . TETJTBBN 4 2 0

Contributions to the Chemistry of Trifluoromethyl-seleninic Acid, Redox Processes in the r 3 CSe(0 ) O S C F n C l 3 -n System (In German) A . D A R M A D I , A . H A A S , and K . T E B B E 4 2 6

Reactions of (T7-C5H 5 )CO(CO)2 and (ry-EtMe4C5)Co(CO)2 with Iodine and Cyanogen Hahdes, X C N ( X = B r O R I ) M . M O R I N 4 3 1

Reactions of Biscyclopentadienyl Vanadium with N O and X N O ( X = C I O R Br) M . M O R X N and M. G A Y O S O 4 3 4

5-Chloro-5-phenyl-l-oxa-4,6-dithia-5-stannocane, a Diplanar Transition State for the Racemisation of the Boat-Chair Conformation in an Eight-Membered Ring ( In German) M . D R A G E R 4 3 7

Polymeric Dimethyl- andDiphenylglyoximato Com­plexes of Cobalt and Iron with Pyrazine as a Bridging Ligand. The Crystal Structure of Bis -(dimethylglyoximato)pyrazine Cobal t ( I I ) +

( I n German) F . K T J B E L and J . S T R A H L E 4 4 1

Isolable Chloro[(thio)alkoxy]triorganylphos-phoniumchlorides as Intermediates of the Oxirane

(Thiirane)-Halogenation with Dichlorophospho-ranes ( In German) R . A P P E L and V . I . G L A S E L 447

Carbonylvanadium, -manganese and -molybdenum Complexes of the Ligands o - C e H 4 E P h 2 ( E , P h 2 ) (Ε, E ' = P , As, Sb, Bi) and a 5 - P h 2 P C H = C H P P h 2

( In German)

R . Τ A L A Y and D . R E H D E R 451

On the R a r e - E a r t h Pnigochalcogenides L n A s S e R . S C H M E L C Z E R , D . S C H W A R Z E N B A C H , and F . H T J L L I G E R 463

Cychc Boron Derivatives of Biurets J . BiBLAWSKi, K . N I E D E N Z U , A . W E B E R , and W . W E B E R 470

Organometallic Lewis Acids, V . Reactions of CarbonyJ-r^-cyclopentadienyl Molybdenum Tetrafluoroborates (^ 5 -C5H 5 )Mo(CO)2(L)EBF 8

( L = CO, PR3) with Phosphanes and Alkenes ( In German) K . SüNKEL, H . E R N S T , and W . B E C K 474

Electrochemical Syntheses, V I I . Electrochemical Substitution Reactions of M(CO)e-w(PR3)» Complexes (M = Cr, Mo, W ) (In German) J . G R O B E and H . Z B I M E R M A N N 482

A Novel Isomerization of an Electron-Rich Alkene E . L . W E I N B E R G , J . T H . B U R T O N , M. C. B A T R D , and M. H E R B E R H O L D 485

Two-Dimensional ( 2 D - J ) N M R Spectroscopy for Analysis of Isomers and Heterocouplings R . B E N N and W . R I E M E R 488

The Structures of S4N® S3N2O2 and S 4 N 3e

R . G L E I T E R and R . B A R T E T Z K O 492

The Fluctional Behaviour of the P 7 Trianion -A Molecular Orbital Study M. C. B Ö H M and R . G L E I T E R 498

Cyclisation of l-Phenyl-4-carboxymethylmercapto-5-arylazo-hydantoins A . F . A . S H A L A B Y , M. A . A B D E L A Z I Z , and S . S . M. B O G H D A D I > 501

Continued overleaf

T h e Crystal Structure of Potassium-bis(hexa-methylenetetramine) -tris- (isothiocyanato) -cuprate(II)-dihydrate, K[Cu(CeHi2N 4)2(NCS)3] · 2 H 2 0 , a Trigonal B i -pyramidal Cupric Complex ( In German) J . P I C K A R D T 6 4 9

Temperature Dependent E S R Studies on Platinum Pyrimidine " B l u e s " : Evidence for a Structural Instability ? M . S E U L , H . N E U B A C H E R , and W . L O H M A N N 6 5 1

Could Hydrogen Peroxide Photolysis Occur i n the Absence of Transition Metals ? S T . L U M K and J . V E P R E K - S I S K A 6 5 4

O n the Hydration of N-Isomeric 5-Tetrazolecarb-aldehydes D . M O D E R H A C K 6 5 6

Direct Photochemical cis-trane Isomerization with 1 8 5 nm Radiation: A Facile Preparation of cis-Di-tert-butylethylene W . A D A M and F . Y A N Y 6 5 8

I S S N 0340-5087

Contents Ζ. Naturforsch. Vol. 36b, No. 5, May 1981

Original Communications

Contributions to the Chemistry of Phosphorus, 1 0 3 . Tri-ieri-butyl-diphosphaarsa-cyclopropane, ( i . B u P ) 2 ( ^ B u A s ) ( In German) M . B A U D L E R and S . E X A X T T K B 5 2 7

On Aluminium Sulfide: a - A ^ s and AkSsitetr.) ( I n German) H . H A E U S B L E R , A . C A N S I Z , and H . D . L Ü T Z 5 3 2

N M R Spectroscopic Studies on Chalcogen Com­pounds, I I . 1 2 5 T e , 7 7 S e , 19F and 1 8 C Chemical Shifts of CPs Substituted Selenium and Tellurium Compounds ( In German) W . G O M B L E R 5 3 5

Structure and Vibrational Spectrum of the a -Un-decatungstophosphate Na2[N(CH8)4]4HPWn03» · 7 EUO ( In German) J . F U C H S , A . T H I E L E , and R . P A L M 5 4 4

Sulfur-Nitrogen-Compounds, V I I I . Synthesis and Characterization of Some Aromatic Sulfurdi-imines ( I n German) G . B R A N D S and A . G O L L O C H 5 5 1

Addition Compounds of Trimethylstibine Dihalo-genides and Antimony(III) Halogenides ( In German) J . W E R N E R , W . S C H W A R Z , and A . S C H M I D T 5 5 6

(MePNMe) 4 · Mel and (MePNMe) 4 · 2 Mel , a Cyclo-tetra(A3,A3,A3,A5-) and a Cyclotetra(A 3,A 5,A 3,A 5-phosphazane) ( In German) W . Z E I S S , T . K U H N , D . L U X , W . S C H W A R Z , and H . H E S S 5 6 1

Separation of Calcium Isotopes with Cryptand Complexes ( In German) K . G . H E U M A N N and H . - P . S C H I E F E R 5 6 6

Chemistry of Polyfunctional Ligands, 6 4 . On Hydridoiridium(III) Complexes of N,N-Bis -(diphenylphosphino)-^-tolylamine ( In German) J . E L L E R M A N N , L . M A D E R , and K . G E I B E L 5 7 1

Rhodium(I) Catalyzed Asymmetric Hydrogenation of α-Acetamido Cinnamic Acid with Monomeric and Polymeric Aminophosphines ( In German)

U . N A G E L , Η . M E N Z E L , P . W . L E D N O R , W . B E C K , A . G U Y O T , and M. B A R T H O L I N 578

Solvent Effects on the Carbon - 13 N M R Chemical Shifts and Rotational Barriers of N,N-Dimethyl-benzamide - Solvent Enhanced π Polarization C. W . F O N G and H . G . G R A N T 585

On the One and Two-Electron Oxidations of Water-Soluble Zinc Porphyrins i n Aqueous Media M. N E U M A N N - S P A L L A R T and K . K A L Y A N A S U H D A -R A M 596

Energy Turnover of a Reaction between Radical Cation and Radical Anion ( I n German) A . S T A N I E N D A 601

Reactions of Mesoionic Five-Membered Heterocycles with o-Quinonoid Compounds, I V . Mono- and Tricyclic l,3-Thiazolium-4-olates, 1,3-Dithioly-Jium-4-oiates ( In German) W . F R I E D R I C H S E N , W . - D . S C H R Ö E R , I . S C H W A R Z , and Α. B Ö T T C H E R 609

Reactions of Five-Membered Mesoionic Heterocycles with o-Quinonoid Compounds, V . 1,3-Oxazolium-5-olates and l,3-ThiazoHum-5-olates ( In German) W . F R I E D R I C H S E N , I . S C H W A R Z , Β. E P E , and K . - F . H E S S E 622

Cycloadditions with o-Benzoquinone-diimines, V I . Reactions of l,3-Diarylbenzo[c]furans with o-Benzoquinone-diimines. Stable Chair and Boat Conformers in the 5,6,11,12-Tetrahydrodibenzo-[b,f][l,4]diazocin Series ( In German) W . F R I E D R I C H S E N , M. R Ö H E , and T . D E B A E R D E -M A E K E R 632

Notes

On the Crystal Structure of Mixed Phosphate/Sulfate Fluoroapatites ( In German) M. C. A P E L L A and E . J . B A R A N 644

Preparation and Crystal Structure of NaaFeSea ( In German) P . M Ü L L E R and W . B R O N G E R 646

Continued overleaf

Occurrence of iran$-3-Hexenal in TJga%^n^f TJi^^S-ray Structure of gem-NsPsCUiNPPhsJz-Con-Leaves ...·.: . . . . . ;..·;"* 'ίότάΐ8Λ,ϊοη(οί the NPPha Groups Α . E A T A N ATTA and Τ . K A J I W A B A ^ ^ ^ Y ' ^ L . R A M A M U R T H Y , P . R A M A -

'•'%• BRA H M AM, and H . M A N O H A B 765 Studies on Wasp Venom, I . L o w Molecular Weight

Constituents of Venom Sac Extracts bom Para- V x m a u B t l ^ c t i o n o f ( < y .AUyl)manganesepentacar. ^ a m ( In German) ^ - bonyl with Bis(diphenylphosphino).N.methyl

K L I M > W ' I ^ A N O K E , and W . A . K O N I Q 757 ^ α ^ ^ ^

D . ' F L B N S K B , K . B R A N D T , and P . S T O O K 768

Silyl-Assisted Ether Cleavage i n Radical Cations of Hydroxylamine Derivatives ( I n German) B . C I O M M E R , H . S C H W A R Z , A . M A A R O T J F I , M . T . R E E T Z , and K . L E V S B N 771

Notes Solvent Effects on the I R Spectra of N-Methylacet-

amide J . MANZTJR and G . G O N Z A L E Z 7 6 3

I S S N 0340-5087

Ζ. Naturforsch. Vol, 36b, No. 6, June 1981

Original Communications

The Stabilisation of Tris(hydrazino)phosphane by-Complex Formation ( I n German) H . N Ö T H and V . T H O R N 659

Nitrido Azido Complexes of Molybdenum(VI). Syn­thesis and Crystal Structure of MoNtNaMNCsHs) ( In German) E . S C H W E D A and J . S T R A H L E 662

Perfluoromethyl-ElementLigands, X X V . Organotin Compounds as Reagents, I V : Cleavage Reactions of the Element-Element Bond i n Complexes of the Type M ( C O ) 5 E R 2 E R /

2 and M ( C O ) 5 E R 2 E ' R ' , Respectively, with Trimethylstannane (R, R ' = C H 8 ; Ε = Ρ, A s ; Ε ' « S, Se, T e ; Μ = Cr, Mo) ( I n German) J . G R O B E and D . L E V A N 666

Ohgophosphine Ligands, I I I . Bis(3-diphenylphos-phinopropyl)phenylphosphinechloroiridium(I) and its Carbonyl and Hydride Derivatives ( In German) E . A R P A O and L . D A H L E N B U R G 672

Coordination Complexes of Reduced Pyrazine and Alky l Derivatives of Boron, Aluminum, Gallium, and Indium ( In German) W . K A I M 677

On the Mechanism of the Formation of Nitrosyl-vanadium Complexes from Hydroxylamine: Reversible, Intramolecular Conversion of Co­ordinated Nitric Oxide to a Hydroxylamido( l—) Ligand ( In German) K . W I E G H A R D T and U . Q T H L T T Z S C H 683

Tl 2 SnÄ, a Thallium(I) Thiostannate(IV) with Five­fold Coordinated T i n ( I n German) G. E U L E N B E R G E R 687

Investigations on the Course of the Hydrolysis of Some Tris(alkoxy)boranes and the Identification of Intermediates ( In German) K . - P . S T E I N F E L D T , G . H E L L E R , and R . B A U ­M E R T 691

Lanthanide(III ) Complexes of Oxamic A c i d S. P . P E R L E P E S , T H . F . Z A F T R O P O U L O S , J . I L K O U T N I S , and A. G . G A U N O S 697

1 0 B , H B , 1 8 C N M R Studies of cfoso-Pentaalkyl-1,5-dicarbapentaboranes(5) ( In German) R . K Ö S T E R and B . W R A O K M E Y E R 704

Organometalphosphine-Substituted Transition Metal Complexes, X X V I I . Reactions of Penta-carbonylmanganese- and Pentacarbonylrhenium-bromide with Organoelement(IVb) Phosphines ( I n German) H . S C H U M A N N and H . N E U M A N N 708

Investigation on Autoxidation of Metallic Copper and Copper(I) Compounds by Different Methods ( In German) L . H O R N E R and E . P L T E F K E 713

Stereoisomerism of 5-Benzylidenetetramic Acids ( In German) H . - D . S T A C H E L and H . P O S C H E N R I E D E R 721

Crystal Structure and the Radiation-Induced Free-Radical Chain Reaction of 2-Oeoxy-β ~O-erythro-pentopyranose in the Solid State Μ. N . S C H U C H M A N N , C. V O N S O N N T A G , Y l - H . T S A Y , and C. K R Ü G E R 726

Phosphate Production and Analysis in the Non-Enzymatic Activation of Amino Acids by A T P when Using Hydroxylamine as a Trapping Agent D . W . M U L L E N S ( J R . ) and J . C. L A C E Y ( J R . ) 732

Solvent Induced Circular Dichroism in Conforma­tional Analysis: Bile Pigments H . L E H N E R , C. K R A U S S , and H . S C H E E R 735

Benzoylation of 3-Substituted 4-Hydroxy-2-quino-lones and 4-Hydroxycoumarines ( In German) W . S T A D L B A U E R and T H . K A P P E 739

Pseudobases from Quinolinium-Salts and Alcoxides ( In German) W . - H . G Ü N D E L and H . B E R E N B O L D 745

Selective Succinylation of Adenosine Catalyzed by 4-Morphohne-N,N /-dicyclohexylcarboxamidine C. S A U E R and U . S C H W A B E 750

Solvent Induced Circular Dichroism in Conformational Analysis: Bile Pigments H a r a l d Lehner* I n s t i t u t für Organische Chemie der Universität Wien , Währingerstraße 38, Α-1090 Wien

Corinna Krauss and Hugo Scheer Botanisches Inst i tut der Universität München, Menzingerstraße 67, D-8000 München 19

Z . Naturforsch. 36b, 735-738 (1981); received November 21, 1980

Solvent Induced Circular Dichroism, Conformation, Enant iomerizat ion , Purpurines , Bilatrienes

T h e applicability of solvent induced circular dichroism ( S I C D ) for the conformational analysis of bile pigments has beon investigated. T h e S - ( — ) - e t h y l lactate induced rotational strengths for octaethylbilindion (4) and its dihydroderivative 5 are remarkably high. R e l a t e d compounds, e.g. the isomeric purpurines 1 and 2 and formyltripyrrinon 3 exhibit a n optical act iv i ty which is smaller by more than one order of magnitude. 1-3 are essen­t ial ly free from steric strain so that a flat arrangement of the chromophore is most l ikely. O n the other hand the closed conformations of 4 and 5 experience considerable steric repulsion of thoir terminal rings, so that a helical topology is energetically favoured. T h i s distinction is reflected in the magnitude of the S I C D observed and demonstrates its applicabil ity for the conformational analysis of bile pigments.

Introduction

Recently it has been shown that S I C D of bile pigments can be useful in their conformational analysis. Thus, for all-Z-all-syn biliverdindimethyl-ester (6) and the X I I I α isomer, for which a helical conformation has been established by various methods [1-5], a remarkably large Δ ε-value is observed in S-(—)-ethyl lactate [3, 5], while for an Ε,Ζ,Ζ isomer [6] no S I C D could be observed under the same conditions. Hence, S I C D seems an attrac­tive method in conformational analysis. I n this report more direct evidence is given for this empirical approach. I t will be shown, that under appropriate conditions this method is useful for bile pigments in general.

Materials and Methods Compounds 1-3 [7], 4 and 5 [8] and 6 [3] were

prepared according to the literature. C D spectra were recorded on a Jobin Y v o n Mark I I I instrument in thermostated ( ± 1 ° ) quartz cuvettes of variable path length (0,01-2,0 cm) and c = l O - ^ l O " 5 Μ. Ab­sorption spectra were measured on a Cary 15 spectrometer in 0,5 cm quartz cuvettes at ambient temperature. (S-(—)-ethyl lactate ([a]f? = —11,1°, neat) was purchased from F l u k a and distilled twice over a Vigreux column prior to use.

* R e p r i n t requests to D r . H . L e h n e r . 0340-5087/81/0600-0735/? 01.00/0

Results and Discussion

Since the magnitude of the S I C D observables is dependent on the inducibility of the optically active solvent employed [5], measurements routinely were performed in S-(—)-ethyl lactate at 20 °C. The S I C D effects exhibited by the pigments 1-6 in the spectral region 300-800 nm are outlined in Table I .

The induced optical activities of the purpurines 1 and 2 as well as that of the formyltripyrrinon 3 are exceedingly small, while the data obtained for all-Z-octaethylbilindion 4 closely resemble those of all-Z-all-syn-biliverdin-IXa-dimethylester (6) exhibiting an induced optical activity of Δ ε — +5 ,9 and —2,9 at 377 and 680 nm, respectively [5]. Likewise, the ellipticities observed for the dihydroderivative 5 (c/. Table I ) are similar to the values reported for the structurally related racem. phytochromobilin-dimethylester [9]. These results are in agreement with geometric considerations. There is one striking difference between the two groups of compounds 1-3 and 4-6, respectively. I n the compounds 1 and 2 a planar structure of the chromophore is readily accessible due to a lack of steric hindrance between rings A and D. I n contrast to the situation in bilatrienes the fourth ring A of the purpurines has virtually no influence on the conformation of the connected chromophore consisting of rings B , C, D . Similar arguments hold for 3, as its molecular skeleton involves only three pyrrolic units. A planar,

736 Η. L e h n e r et al. · Solvent I n d u c e d Circular Dichroism

Table I . Δ em ax-values [ Μ - 1 c m - 1 ] of the bile pigments 1-6 in S - ( — ) - e t h y l lactate at 20 °C determined at the wavelength λ ([nm]).

1 2 3 4 5* 6*

4- 0,2 (550) — 0,2 (500)

— 0,2 (540) — 0,2 (510) — 3,4 (667) + 6,9 (366)

— 5,2 (610) + 8,7 (348)

— 2,9 (675) + 5,9 (378)

a T h e corresponding d a t a for the two synthetic isomeric phytochromobilin-dimethylesters are reported to be + 5,1 (372) and — 2 , 6 (610) a n d + 3,5 (375) and — 2 , 2 (610), respectively [9]. (The values at 610 n m do not represent the m a x i m u m of the long wavelength band but the edge of the recorded wavelength range.)

b Values taken from ref. [5 ] ; for the temperature dependence cf. F i g . 1.

closed conformation has been suggested for 3 in related compounds such as 4 and 5 into a helical solution [ 1 0 ] and has been determined in the crystal arrangement. 4 - 6 can flip between two enantiomeric state of an analogue [ 1 1 ] . B y contrast, the non- sets of conformations, which are both inherently bonded-interactions between the peripheral rings chiral and separated by an activation barrier of force all-Z-all-syn-biliverdindimethylester (6 ) and approx. 4 2 kJ/mol [ 1 2 ] .

1 2 ! C - 4 - ep imer

COOCH* COOCH,

5 6

Η. L e h n e r et al. · Solvent I n d u c e d Circular Dichroism 737

The finding of a large S I C D in the twisted species of 4—6 is reminiscent of the effects observed in natural optical activity: the rotational strengths of inherently chiral chromophores are generally larger than the pertinent values for chirally perturbed symmetrical chromophores [13, 14].

Hence, the large S I C D of 4-6 as compared to 1-3 is rationalized by the induction of an excess popula­tion of one enantiomeric helix, which originates from diastereomeric interactions of the optically active solvent with easily interconverting antipodal conformations of the solute. Therefore the equi­librium constant between P- and M-helices is no longer unity, but is shifted to the one or other side, so that one enantiomeric, inherently chiral species predominates. Thus, this process represents an asymmetric transformation of the first kind or enantiomerization [15]. A similar mechanism has been suggested for the intense C D in bilirubin and biliverdin induced by binding to serum albumen [16, 17].

Of course, the amount of the excess population in a given optically active solvent is not known, and it is even probable that the solute involves an ensemble of different diastereomeric conformations. I n other words, although a large induced ellipticity as compared to a related non-helical molecule is indicative of a considerable amount of twisted conformers in the sample, it is by no means a proof for conformational homogeneity. For 6 e.g. it has been shown by fluorescence spectroscopy that its solvatochromic and thermochromic properties are due to different populations of coiled and stretched conformers [5]. Accordingly, on lowering the tem­perature the amount of the coiled species of 6 should increase. I n fact, the S I C D of 6 in ethyl lactate exhibits an extraordinarily strong temperature dependence with respect to the intensity, whereas the position and shape of the band remains un­changed (c/. F ig . 1). The increase of the effect on lowering the temperature reflects a shift of the conformational equilibrium to helical species, which exhibit a much larger contribution to the S I C D observed than other conformers. The dependence of an induced C D on the conformation of the substrate has further been supported by incubation of 6 in liposomes of optically active lecithines [18]. I n this matrix 6 exhibits chronochromic properties, which are due to a conformational transition [19].

X . n m

F i g . 1. S I C D in the V I S absorption region of 6 in S - ( — ) - e t h y l lactate (10~ 4 M) at 35 °C ( ), 20 °C ( ), and 9 °C ( ). T h e temperature-dependence observed is fully reversible.

On the basis of these considerations the small S I C D of 1-3 is not surprising. The arguments given above explain as well the negligible S I C D of Ε,Ζ,Ζ-biliverdin [6], in which the steric repulsion between the peripheral rings is removed and of a biliverdin bridged between N-21 and N-24, in which the ready interconversion between enantiomeric helices is hindered at ambient temperature [20].

Concluding Remarks

I n order to identify twisted chromophore con­formations by means of S I C D the induced rotational strength of a related molecule with a similar chromophore of established conformation should be known. A chromophore independent criterion based on the anisotropy factor (g), which has been fruit­fully applied in natural optical activity [14], cannot be given.

Although the electronic transitions stemming from helical conformations of 4-6 and other bi-latrienes should be electrically and magnetically allowed the condition g * 1 0 - 2 [14] will scarcely be met. E v e n in the case of conformational homo­geneity the enantiomeric excess population -the analogue of "enantiomeric purity" in natural optical activity - will not necessarily reach unity. Its value is not known for any given case, and it additionally changes with the optically active solvent employed.

This work has been supported by the "Fonds zur Förderung der wissenschaftlichen Forschung in Österreich" (project 3033), by the "Hochschul-jubiläumsstiftung der Stadt W i e n " and by the "Deutsche Forschungsgemeinschaft", Bonn, B a d Godesberg. We thank Ms. C. Bubenzer for skillful technical assistance.

738 Η. L e h n e r et cd. · Solvent Induced Circular D i c h r o i s m

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[2] H . L e h n e r , S . E . B r a s l a v s k y , and K . Schaffner, Angew. C h e m . 90, 1012 (1978); Angew. Chem. , I n t . E d . E n g l . 17, 18 (1978).

[3] H . L e h n e r , S . E . B r a s l a v s k y , and K . Schaffner, Liebigs A n n . Chem. 1978, 1990.

[4] H . F a l k , K . G r u b m a y r , E . Haslinger, T . Schle-derer, and K . T h i r r i n g , Monatsh. Chem. 109, 1451 (1978).

[5] S . E . B r a s l a v s k y , A . R . H o l z w a r t h , E . Langer, H . L e h n e r , J . I . Matthews, and K . Schaffner, I s r . J . C h e m . 20, 196 (1980).

[6] A . Gossauer, M . B l a c h a - P u l l e r , R .Zeisberg , and V . W r a y , Liebigs A n n . C h e m . 1981, 342.

[7] H . Scheer, U . Linsenmeier , and C. Krause , Hoppe-Seyler 's Z . P h y s i o l . C h e m . 358, 185 (1977).

[8] J . A . S . Cavaleiro and Κ. M . Smith , J . Chem. S o c , P e r k i n T r a n s . I 1973, 2149.

[9] J . P . Weller and A . Gossauer, Chem. Bor. 113, 1603 (1980).

[10] H . Scheer and W . K u f e r , Z . Naturforsch. 82c, 513 (1977).

[11] D . L . Cul len , F . E . Meyer , F . E i v a z i , and Κ. M. S m i t h , J . C h e m . S o c , P e r k i n I I 1978, 259.

[12] H . L e h n e r , W . R i e m e r , and K . Schaffner, Liebigs A n n . Chem. 1979, 1798.

[13] F . Ciardelli and P . Salvadori , F u n d a m e n t a l Aspects and R e c e n t Developments in Opt ical R o t a t o r y Dispersion and Circular D i c h r o i s m ; H e y d e n , L o n d o n 1973.

[14] G . Snatzke , Angew. C h e m . 91, 380 (1979); Angew. C h e m . I n t . E d . E n g l . 18, 363 (1979).

[15] Ε . E . T u r n e r and Μ. M. H a r r i s , Quart . R e v . C h e m . Soc. 1, 299 (1974); cf. also B . Bosnien , in ref. [13], p. 254.

[16] G . Wagniere and G . Blauer , J . A m . C h e m . Soc. 98, 7806 (1976).

[17] G . B lauer and G . Wagniere, J . A m . Chem. S o c 97, 1949 (1975).

[18] I . - M . T e g m o - L a r s s o n , S. E . B r a s l a v s k y , C. Nico-l a u , and K . Schaffner, B iochim. Biophys . A c t a , in press.

[19] I . - M . Togmo-Larsson , S. E . B r a s l a v s k y , S . Culshaw, R . E l l u l , C. Nicolau, and K . Schaffner, in preparation.

[20] Η. F a l k and Κ. T h i r r i n e , Tetrahedron 37, 761 (1981).