A Specialist Periodical Report

OrganometallicChemistryVolume 5

A Review of the Literature Published during 1975

Senior ReportersE. W. Abel, Department of Chemistry, University of Exeter

F. G. A. Stone, Department of Inorganic Chemistry, University of Bristol

ReportersT~ S. Abram, New University of UlsterD. A. Armitage, Queen Elizabeth College, University of LondonB. L. Booth, University of Manchester Institute of Science and TechnologyD. J. Cardin, Trinity College, DublinN. G. Connelly, University of BristolJ. A. Connor, University of ManchesterM. Cooke, University of BristolD. A. Edwards, University of BathS. K. Gupta, Pfizer lnc., Groton, Connecticut, U.S.A.J. A. S. Howell, University of KeeleJ. P. Maher, University of BristolT. P. Onak, California State University, Los Angeles, California, U.S.A.A. D. Redhouse, University of Salfords. D. Robinson, King's College, University of LondonJ. L. Wardell, University of AberdeenW. E. Watts, New University of UlsterC. White, University of Sheffield

© Copyright 1976

The Chemical SocietyBurlington House, London W1V OBN

ISBN: 085186541 0ISSN: 0301-0074

Library of Congress Catalog Card No. 72-83459

Printed in Great Britain by

Adlard & Son Ltd.Bartholomew Press, Dorking

A Specialist Periodical Report

OrganometallicChemistryVolume 5

A Review of the Literature Published during 1975

Senior ReportersE. W. Abel, Department of Chemistry, University of Exeter

F. G. A. Stone, Department of Inorganic Chemistry, University of Bristol

ReportersT~ S. Abram, New University of UlsterD. A. Armitage, Queen Elizabeth College, University of LondonB. L. Booth, University of Manchester Institute of Science and TechnologyD. J. Cardin, Trinity College, DublinN. G. Connelly, University of BristolJ. A. Connor, University of ManchesterM. Cooke, University of BristolD. A. Edwards, University of BathS. K. Gupta, Pfizer lnc., Groton, Connecticut, U.S.A.J. A. S. Howell, University of KeeleJ. P. Maher, University of BristolT. P. Onak, California State University, Los Angeles, California, U.S.A.A. D. Redhouse, University of Salfords. D. Robinson, King's College, University of LondonJ. L. Wardell, University of AberdeenW. E. Watts, New University of UlsterC. White, University of Sheffield

© Copyright 1976

The Chemical SocietyBurlington House, London W1V OBN

ISBN: 085186541 0ISSN: 0301-0074

Library of Congress Catalog Card No. 72-83459

Printed in Great Britain by

Adlard & Son Ltd.Bartholomew Press, Dorking

Foreword

This Volume of the Specialist Periodical Reports 'Organometallic Chemistry'reviews the literature of the calendar year 1975. A significant addition is the inclusionof a short chapter on the biological aspects of organometallic chemistry. In order tokeep the volumes in this series to a reasonable size, it is becoming increasinglynecessary to arrange for our Reporters to place at the end of their chapters biblio­graphies of papers not reviewed in the cursive text. In this way essentially completecoverage of the literature is maintained, without producing volumes in excess of500 pages.

The year 1975 was marked by the publication of several articles and books likelyto be of lasting value. Volume 100 of the Journal of Organometallic Chemistryappeared with accounts of their own work by H. C. Brown, J. Chatt, F. A. Cotton,C. Eaborn, E. O. Fischer, H. Gilman, M. F. Hawthorne, R. B. King, M. Kumada,M. F. Lappert, A. N. Nesmeyanov, J. G. Noltes, H. Normant, R. Pettit, O. A.Reutov, D. Seyferth, F. G. A. Stone, G. Wilkinson and G. Wittig.

Volumes in the series of monographs concerned with organometallic chemistry,published by Academic Press, continue to appear. It is useful to summarize inreverse chronological order the titles which have been published so far.

1. Organochromium Compounds, R. P. A. Sneeden, 1975.2. Organoborane Chemistry, T. Onak, 1975.3. The Organic Chemistry of Nickel, Volume 2, Organic Syntheses, P. W. Jolly

and G. Wilke, 1975.4. Zerovalent Compounds of Metals, L. Malatesta and S. Cenini, 1974.5. Metal Carbonyl Spectra, P. S. Braterman, 1974.6. Organometallic and Co-ordination Chemistry of Platinum, U. Belluco, 1974.7. Organometallic Chemistry of Titanium, Zirconium and Hafnium, P. C.

Wasler, R. S. P. Coutts and H. Weigold, 1974.8. The Organic Chemistry of Nickel, Volume 1, Organonickel Complexes,

P. W. Jolly and G. Wilke, 1974.9. Organotransition Metal Chemistry; A Mechanistic Approach, R. F. Heck,

1974.10. Organometallic Reaction Mechanisms of the Nontransition Elements, D. S.

Matteson, 1974.11. The Organic Chemistry of Palladium, Volumes 1 and 2, P. M. Maitlis, 1971.12. Carboranes, R. N. Grimes, 1970.13. The Chemistry of Organotin Compounds, R. C. Poller, 1970.14. Electronic Transitions in Organometalloids, B. G. Ramsey, 1969.

iv Foreword

A review symposium to commemorate Walter Hieber's seminal contributions tometal carbonyl chemistry was held in Ettal in July 1974. Some of the paperspresented at this meeting were published in J. Organometallic Chem., Vol. 94. Wedraw particular attention to an account by H. Behrens of the life work of W. Hieber.

May 1976 E. W. AbelF. G. A. Stone

Contents

Chapter 1 Group I: The Alkali and Coinage MetalsBy J. L. Wardell

1 Alkali-metal Chemistry 1

Alkali-metal Compounds with Aromatic Hydrocarbons 1Radical Anion and Dianion Salts 1Alkali-metal Fluorenyl and Related Compounds 2

Alkali-metal Allylic, Alkenyl, and Alkynyl Compounds 5Alkali-metal Alkyl and Aryl Compounds 8Carbenoid Species 11

2 The Coinage Metals 11

General 11Copper 13

n-Bonded Compounds 13a-Bonded Compounds 14

Gold 15

3 Appendix 16

Chapter 2 The Alkaline Earths and Zinc and its Congeners 19

By J. L. Wardell

1 Beryllium 19

2 Magnesium 19

Grignard Formation 19Compounds 20ComplexesReactions

Rearrangements and Additions to Alkenes 22Reactions with Ketones 25Other Reactions 26Transition-metal-catalysed Reactions 27

3 Calcium, Strontium, and Barium 28

vi Contents

4 Zinc and Cadmium 29

5 Mercury 31

General 31Per- and Poly-halogeno-organomercury Compounds 32Oxymercuration Studies 33Methylmercury Compounds 35Other Exchange Processes 36Mercury-Carbon Cleavage 36Symmetrization 36General N.M.R. Spectroscopic Studies 37

6 Appendix 37

Chapter 3 Group III: Boron 39

By S. K. Gupta

1 Books and Reviews 39

2 Boranes 40

Preparation 40Reactions 43

Hydroboration 43Polar Reactions of Boron Compounds 44Radical and Photochemical Reactions of Boron

Compounds 50Allylborane Chemistry 51Theoretical Aspects 52

3 Borates as Synthetic Intermediates 53

Carbon-transfer Reactions 53Hydride-transfer Reactions 56

4 Boron-containing Cyclic Compounds 59

5 Metal-containing Boron Compounds 60

6 Boron-Nitrogen Compounds 61

7 Structure, Spectroscopy, and Analysis of Boron Compounds 63

Contents vii

Chapter 4 The Carbaboranes, including their Metal Complexes 67

By T. Onak

1 Carbaborane Interconversions 67

2 a-Bonded Derivatives 67

3 Cage Metallocarbaborancs 70

4 Physical and Theoretical Studies 75

5 Reviews and Bibliography 78

Chapter 5 Group III: Aluminium, Gallium, Indium, and Thallium 80

By J. P. Maher

1 Introduction 80

2 Aluminium 80

Preparations, Reactions, and Complexes 80Exchange Reactions, Structures, and Bonding 86Organic Preparative Reactions 89Transition-metal Alane Complexes and Catalysts 91

3 Gallium and Indium 95

Preparations and Physical Properties 95Reactions and Complexes 100

4 Thallium 101

Physical Properties and Preparations 101Complexes 104Organic Preparative Reactions 104

5 Bibliography 107

Chapter 6 Group IV: The Silicon Group IIIBy D. A. Armitage

1 Introduction 111

2 The Carbon-Metal Bond 112

3 Catenation 131

4 Hydrides of Silicon, Germanium, and Tin 134

viii Contents

5 The Radicals R3M· and their Reactions and Metal Derivatives 136

6 Nitrogen Derivatives 139

Polyazo-compounds 143

7 Phosphine and Arsine Derivatives 143

8 Oxygen Derivatives 145

9 Sulphur and Selenium Derivatives 148

10 Halogen Derivatives 149

11 Bibliography 151

Chapter 7 Arsenic, Antimony, and Bismuth 157

By J. L. Wardell

1 Univalent Species 157As! 157

2 Tervalent Species 157

Arsenic Ylides 161Arsonium Salts 162

3 Quinquevalent Species 162

4 Bibliography 164

Chapter 8 Metal Carbonyls 166

By E. W. Abel and F. G. A. Stone

1 Introduction 166

2 Lr. Spectroscopy and Matrix-isolation Studies 167

3 13CN.M.R. Studies and CO Ligand Site Exchange inPolynuclear Structures 168

4 Electron Spectra 170

5 Molecular Structure Determination by X-Ray Crystallography 171

6 Chemical Reactions and New Compounds 172

Contents ix

Chapter9 Organometallic Compounds containing Metal-MetalBonds 176

By N. G. Connelly

1 Compounds containing Bonds between Transition Metals 176

Homonuc1ear Bonds between Transition Metals 176Niobium and Tantalum 176Chromium, Molybdenum, and Tungsten 177Manganese, Technetium, and Rhenium 178Iron 179Ruthenium and Osmium 184Cobalt 186Rhodium and Iridium 189Nickel, Palladium, and Platinum 191Copper, Silver, and Gold 192

Heteronuc1ear Bonds between Transition Metals 192

2 Compounds containing Bonds between Transition Metals and theElements of Groups lA, IIA and IIIB-VB 195

Group IA 195Group IIA 195Group BIB 196Group IVB 197

Spectral Studies 197Titanium 197Vanadium 197Chromium, Molybdenum, and Tungsten 197Manganese 198fion 199Ruthenium and Osmium 199Cobalt and Rhodium 201Nickel and Platinum 201

Group VB 201

3 Compounds containing Group lIB-Group IVB Element Bonds 202

4 Bibliography 203

Chapter 10 Ligand Substitution Reactions of Metal andOrganometal Carbonyls with Group V and VIDonor Ligands 205

By D. A. Edwards

1 Introduction 205

2 General Papers on Metal Carbonyl Complexes 205

x Contents

3 Groups IV and V 207

4 Group VI 208

Carbonyl Complexes of Cr, Mo, and W 208Cyclopentadienyl Carbonyl and Related Complexes

of Cr, Mo, and W 218

5 Group VII 221

Cyclopentadienyl Carbonyl and Related Complexes 221Other Group VII Complexes 223

6 Group VIII: Fe, Ru, and Os 231

Cyclopentadienyl Carbonyl and Related Complexes 231Other Fe Carbonyls 233Other Ru and Os Carbonyls 235

7 Group VIII: Co, Rh, and Ir 237

Cobalt Complexes 237Rhodium and Iridium Complexes 238

8 Group VIII: Ni, Pd, and Pt 242

9 Copper 242

10 Reviews 243

11 Bibliography 243

Chapter 11 Carbene and Carbyne ComplexesBy J. A. Connor

1 Introduction

2 Synthesis of Carbene Complexes

From a-Alkyl Metal CompoundsFrom Co-ordinated Carbon MonoxideFrom Co-ordinated IsocyanideFrom Co-ordinated AlkynesFrom Heterocyclic PrecursorsFrom Diazoalkane PrecursorsFrom Halogenoalkylamino-compoundsOther Methods

245

245

245

245246247248248249249250

Contents xi

3 Reactions of Carbene Complexes 250

The Mechanism of Olefin Metathesis 253

4 Structure and Bonding in Carbene Complexes 254

Crystallographic Studies 254Spectroscopic Properties 256

5 Carbyne Complexes 256

6 Bibliography 257

Chapter 12 Complexes containing Metal-Carbon a-Bonds 259

By B. L. Booth

1 Reviews 259

2 Binary Alkyl and Aryl Complexes 259

Group IV 259Group V 260Group VI 260Group VII 261Group VIII 261Group I 261

3 Complexes containing Donor Ligands 262

Group VI 262Group VIII 262

Iron Triad 262Cobalt Triad 262Nickel Triad 263

Group I 267

4 Complexes containing Carbonyl or Cyclopentadienyl Groups 269

Cyclopentadienyl Complexes 269Carbonyl Compounds 270Cyclopentadienyl Carbonyl Compounds 274G-Bonded n-Cyclopentadienyl Complexes 278

5 Cyclometallated Complexes 278

Nitrogen Donors 278Phosphorus Donors 280Sulphur and Oxygen Donors 282Other Examples of Metal-Carbon G-Bonds Stabilized by the

Chelate Effect 284

xii Contents

6 Insertion Reactions 286

Olefin and Acetylene Insertion into Metal-Hydrogen Bonds 286Olefin and Acetylene Insertion into Metal-Carbon Bonds 287Carbon Monoxide Insertion (and De-insertion) 288Sulphur Dioxide Insertion 289Other Insertion Reactions 289

7 Nucleophilic Attack on Co-ordinated Ligands 290

Chapter 13 Hydrocarbon-Metal 7T-Complexes 292By J. A. S. Howell

1 Reviews 292

2 Complexes derived from Mono-oleflns 292

Copper, Silver, and Gold 292Zerovalent Nickel, Platinum, and Palladium 292Bivalent Nickel, Platinum, and Palladium 293Cobalt Rhodium, and Iridium 296Iron, Ruthenium, and Osmium 298Chromium, Molybdenum, and Tungsten 300Other Metals 300

3 Complexes derived from Chelating Unconjugated Dienes andPolyolefins 301

Nickel, Platinum, and Palladium 301Rhodium and Iridium 305Iron and Ruthenium 306Chromium, Molybdenum, and Tungsten 306Other Metals 307

4 Complexes derived from Chelating Conjugated Dienes andPolyolefins 307

Acyclic Olefins 307Cyclic Dienes and Polyolefins, including Trimethylene-

methane Complexes 311Iron, Ruthenium, and Osmium 311Chromium, Molybdenum, and Tungsten 316Titanium 318Other Metals 318

5 Complexes derived from Acetylenes 320

6 Polynuclear Complexes 326