Volume8

Mechanisms of Inorganic and Organometallic Reactions

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VolumeS

Mechanisms of Inorganic and Organometallic Reactions

Edited by

M. V. Twigg Johnson Matthey Royston, Hertfordshire, England

SPRINGER SCIENCE+BUSINESS MEDIA. LLC

The Library of Congress has cataloged this serial title as follows:

Mechanisms of inorganic and organometallic reactions.- Voi. 1-

v.: ill.; 24cm. Editor: M. V. Twigg. ISSN 0740-8900 = Mechanisms of inorganic and organometallic reactions.

1. Chemical reactions-Collected works. 2. Chemistry, lnorganic-Collected works. 3. Organometallic chemistry-Collected works. 4. Organometallic com­pounds-Collected works. 1. Twigg, M. V. QDS01.M42S S41.3'9'.0S-dcl9 87-648073

AACR 2 MARC-S Library of Congress [8706]

ISBN 978-1-4899-1626-6 ISBN 978-1-4899-1624-2 (eBook) DOI 10.1007/978-1-4899-1624-2

© 1994 Springer Science+Business Media New York Originally published by Plenum Press, New York in 1994 Softcover reprint ofthe hardcover 1st edition 1994

Ali rights reserved

No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher

Contributors

M. Bochmann School of Chemical Sciences, University of East Anglia, University Plain, Norwich NR4 7TJ, U.K.

J. Burgess Chemistry Department, The University, Leicester LEl 7RH, U.K.

E. C. Constable University Chemical Laboratory, Cambridge CB2 lEW, U.K.; present address: lnstitut fiir Anorganische Chemie, Universitiit Basel, CH-4056 Basel, Switzerland.

R. J. Cross Chemistry Department, University of Glasgow, Glasgow, Scotland G12 8QQ, U.K.

R. van Eldik Institut fiir Anorganische Chemie, Universitiit Witten/ Herdecke, 58448 Witten, Germany

J. F. Endicott Department of Chemistry, Wayne State University, Detroit, Michigan 48202

R. W. Hay Chemistry Department, University of St. Andrews, St. Andrews, Scotland KY16 9ST, U.K.

D. A. House Chemistry Department, University of Canterbury, Christchurch 1, New Zealand

L.A. P. Kane-Maguire Chemistry Department, Wollongong University, Wollongong, NSW 2500, Australia

A. G. Lappin Department of Chemistry, University of Notre Dame, Notre Dame, Indiana 46556

v

vi Contributors

D. H. Macartney Department of Chemistry, Queen's University, Kingston, Ontario K7L 3N6, Canada

A. Neubrand Institut fiir Anorganische Chemie, Universitat Witten/ Herdecke, 58448 Witten, Germany

K. G. Orrell Chemistry Department, University of Exeter, Exeter, Devon EX4 4QD, U.K.

R. D. Pike Department of Chemistry, College of William and Mary, Williamsburg, Virginia 23185

A. J. Poe Chemistry Department, University of Toronto, Toronto, Ontario M5S lAl, Canada

K. Scharfenkamp Department of Chemistry, Wayne State University, Detroit, Michigan 48202

G. Steadman Chemistry Department, University College of Wales, Swansea, Wales SA2 8PP, U.K.

P. A. Tregloan School of Chemistry, University of Melbourne, Parkville 3052, Australia

R. M. L. Warren Department of Chemistry, University of Notre Dame, Notre Dame, Indiana 46556

M.A. Watzky Department of Chemistry, Wayne State University, Detroit, Michigan 48202

Preface

Mechanisms of Inorganic and Organometallic Reactions provides an ongoing critical review of the primary literature concerned with mechanisms of inorganic and organometallic reactions. The main focus is on reactions in solution, although solid-state and gas-phase studies are included where they provide relevant mechanistic insight.

Each volume covers an eighteen-month literature period, and this, the eighth volume in the series, includes papers published during January 1990 through June 1991. Where appropriate, references to earlier reports and to specific sections in previous volumes are given. Coverage spans the whole area as comprehensively as possible in each volume, and while it is impossible to be absolutely exhaustive, every effort is made to include all of the important published work that is relevant to the elucidation of reaction mechanisms.

Numerical data are reported in the units used by the original authors, and they are converted to common units only when comparisons are being made. The successful format of earlier volumes is retained to facilitate tracing progress over several years in a particular topic, and the series now permits this to be done for a twelve-year period. The introduction three volumes ago of computerized techniques to improve cross-referencing in the Index brought positive reader comments, and their use is being continued.

The amount of work published continues to increase. As a result, the effort involved in collecting and critically selecting references for inclusion, as well as actually writing the chapters, is increasing. All the contributors are sincerely thanked for expending this effort while keeping high standards of scholarship. The vital support and the helpfulness of all those associated with the publication process at Plenum are also very much appreciated.

vii

viii Preface

Thanks are also due for the support and encouragement of readers who send reprints or preprints of papers, or offer comments and advice. As always, these are most welcome.

M. V. Twigg

Contents

Part I. Electron Transfer Reactions

Chapter 1. Electron Transfer: General and Theoretical

J. F. Endicott, J. W. Scharfenkamp, and M. A. Watzky

1.1. General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 1.2. Electronic Coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 1.3. Coupling between Electron Transfer Rates and Solvent

Dynamics .. .. .. . . . . . . .. .. . . . .. . . . .. . . . . . .. . . . . .. .. . . . . .. 5 1.4. Intervalence and Related Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

Chapter 2. Redox Reactions between Two Metal Complexes

D. H. Macartney

2.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2.2. Reactions of Metal Aqua and Oxo Ions . . . . . . . . . . . . . . . . . . . . . . 7

2.2.1. Titanium ............................. ; . . . . . . . . . . . . 7 2.2.2. Chromium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 2.2.3. Iron . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 2.2.4. Molybdenum and Tungsten . . . . . . . . . . . . . . . . . . . . . . . . . . 20

ix

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2.3. Reactions of Metal Ion Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . 21 2.3.1. Chromium, Molybdenum, and Tungsten............... 21 2.3.2. Iron, Ruthenium, and Osmium . . . . . . . . . . . . . . . . . . . . . . . 22 2.3.3. Cobalt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 2.3.4. Nickel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25 2.3.5. Copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25 2.3.6. Actinides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 2.3. 7. Stereoselective Electron Transfer . . . . . . . . . . . . . . . . . . . . . 26

2.4. Reactions with Metalloproteins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 2.4.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 2.4.2. Copper Proteins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27 2.4.3. Hemoglobin and Myoglobin . . . . . . . . . . . . . . . . . . . . . . . . . 28 2.4.4. Cytochromes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28 2.4.5. Iron-Sulfur Proteins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29

Chapter 3. Metal-Ligand Redox Reactions

R. M. L. Warren and A. G. Lappin

3.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31 3.2. Reactions with Oxygen, Hydrogen Peroxide, and Water . . . . . . . . 31 3.3. Oxo-Transfer Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 3.4. Halides, Halogens, and Halogenate Ions . . . . . . . . . . . . . . . . . . . . . 35 3.5. Sulfur-Containing Reagents: S 2 0~-. so~-. and Thiols......... 37 3.6. Nitrogen-Containing Reagents: NO] and N 2 • • • • • • • • • • • • • • • • • 38 3.7. Phosphorus and Arsenic Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . 40 3.8. Reduction of Carbon Dioxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40 3.9. Alcohols, Acids, Ascorbate, and Quinols . . . . . . . . . . . . . . . . . . . . . 41 3.10. Alkanes and Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 3.11. Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 3.12. Reactions Involving Metal Ion Reduction and Radical Reactants 44

Part II. Substitution and Related Reactions

Chapter 4. Reactions of Compounds of the Nonmetallic Elements

G. Steadman

4.1. Boron ......... ~........................................ 49 4.2. Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52

(;ontents xi

4.3. Silicon .................. ; . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52 4.4. Germanium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57 4.5. Nitrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57 4.6. Phosphorus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62 4.7. Arsenic and Antimony . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67 4.8. Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67 4.9. Sulfur . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68 4.10. Selenium and Tellurium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71 4.11. Halogens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72

4.11.1. Fluorine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72 4.11.2. Chlorine and Bromine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72 4.11.3. Iodine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73

4.12. Oscillating Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74

Chapter 5. Ligand Exchange Reactions of Inert-Metal Complexes­Coordination Numbers 4 and 5

R. J. Cross

5.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79 5.2. Ligand Exchange at Square-Planar Platinum(II) . . . . . . . . . . . . . . 81 5.3. Ligand Exchange at Square-Planar Palladium(II) . . . . . . . . . . . . . 84 5.4. Reactions of Nickel Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85 5.5. Five-Coordinate Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87 5.6. Three-Coordinate Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89 5.7. Ligand Exchange at Square-Planar Rhodium(!) . . . . . . . . . . . . . . . 90 5.8. Reactions of Planar Complexes of Copper, Silver, and Gold . . . . 91 5.9. Trans Effect.............................................. 92 5.10. Isomerization Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94

Chapter 6. Substitution Reactions of Inert-Metal Complexes­Coordination Numbers 6 and Above: Chromium

D. A. House

6.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97 6.2. Aquation and Solvolysis of Chromium(III) Complexes . . . . . . . . . 98

6.2.1. [CrLmXnJz+ Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98 6.2.2. Cr(III)-C Bond Rupture . . . . . . . . . . . . . . . . . . . . . . . . . . . 100 6.2.3. Dechelation/Chelation Processes ......... :. . . . . . . . . . . 103

6.3. Formation of Chromium(III) Complexes . . . . . . . . . . . . . . . . . . . . . 105

xii Contents

6.3.1. The Nature ofthe CrH Cation in Aqueous Solution..... 105 6.3.2. Anation Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108

6.4. Base Hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108 6.5. Oxidation and Reduction of Cr(III) Complexes . . . . . . . . . . . . . . . 110 6.6. Isomerization and Racemization . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113 6.7. Photochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113 6.8. The Solid State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114

6.8.1. Single-Crystal X-Ray Structures . . . . . . . . . . . . . . . . . . . . . . 114 6.8.2. Synthesis and Solid-State Decomposition . . . . . . . . . . . . . . 125

6.9. Other Oxidation States . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125 6.9.1. Chromium(!) and Chromium(II) . . . . . . . . . . . . . . . . . . . . . 125 6.9.2. Chromium(IV) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128 6.9.3. Chromium(V) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128 6.9.4. Chromium(VI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128

6.10. Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131 6.11. Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131

Chapter 7. Substitution Reactions of Inert-Metal Complexes­Coordination Numbers 6 and Above: Cobalt

R. W. Hay

7.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133 7.2. Base Hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133 7.3. Isomerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135 7.4. Aquation and Solvolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137 7.5. Assisted Aquation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138 7.6. Anation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139 7.7. Carbonato Complexes..................................... 139 7.8. Ligand Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140 7.9. Vitamin B12 • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 140 7.10. Photochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141 7.11. Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142

Chapter 8. Substitution Reactions of Inert-Metal Complexes­Coordination Numbers 6 and Above: Other Inert Centers

J. Burgess

8.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145 8.2. Groups 5 to 7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152

Contents xiii

8.2.1. Vanadium, Niobium, and Tantalum . . . . . . . . . . . . . . . . . . 152 8.2.2. Molybdenum and Tungsten . . . . . . . . . . . . . . . . . . . . . . . . . . 152 8.2.3. Technetium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154 8.2.4. Rhenium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154

8.3. Iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155 8.3.1. Penta-, Hexa-, and Tetracyanoferrates . . . . . . . . . . . . . . . . . 155 8.3.2. Iron(II)-Diimine Complexes . . . . . . . . . . . . . . . . . . . . . . . . . 159 8.3.3. Polydentate, Macrocyclic, and Encapsulating Ligands . . . 163 8.3.4. Iron(III) Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164

8.4. Ruthenium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167 8.4.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167 8.4.2. Solvent Exchange and Replacement . . . . . . . . . . . . . . . . . . . 168 8.4.3. Diimine Complexes................................. 169 8.4.4. Other Nitrogen Donor Ligands . . . . . . . . . . . . . . . . . . . . . . 170 8.4.5. Polyaminocarboxylate Ligands . . . . . . . . . . . . . . . . . . . . . . . 171 8.4.6. Ternary Complexes: Sulfur/Phosphorus/Halide Ligands . . 171 8.4.7. P-Diketonate Ligands............................... 173 8.4.8. Binuclear and Trinuclear Complexes . . . . . . . . . . . . . . . . . . 173

8.5. Osmium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174 8.6. Rhodium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176 8.7. Iridium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177 8.8. Platinum(IV) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178

Chapter 9. Substitution Reactions of Labile Metal Complexes

P. A. Tregloan

9.1. Ligand Substitution on Uni- and Bivalent Metal Ions . . . . . . . . . . 183 9.1.1. Group 1 Ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183 9.1.2. Group 2 Ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188 9.1.3. Uni- and Bivalent First-Row Transition Metal Ions . . . . . 190 9.1.4. Uni- and Bivalent Heavy Transition Metal Ions . . . . . . . . 197

9.2. Ligand Substitution on Trivalent Metal Ions . . . . . . . . . . . . . . . . . 200 9.2.1. Group 3 Ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200 9.2.2. Trivalent First-Row Transition Metal Ions . . . . . . . . . . . . . 202 9.2.3. Trivalent Heavy Transition Metal Ions . . . . . . . . . . . . . . . . 204 9.2.4. Trivalent Lanthanide Ions . . . . . . . . . . . . . . . . . . . . . . . . . . . 205

9.3. Ligand Substitution on Higher-Valency Metal Ions . . . . . . . . . . . . 209 9.3.1. Higher-Valency Metal Ions . . . . . . . . . . . . . . . . . . . . . . . . . . 209 9.3.2. Oxo-Metal Ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209

9.4. Substitution on Binuclear Metal Complexes . . . . . . . . . . . . . . . . . . 211

xiv Contents

Part Ill. Reactions of Organometallic Compounds

Chapter 10. Substitution and Insertion Reactions

A. J. Poe

10.1. Substitution Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215 10.1.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215 10.1.2. Mononuclear Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . 221 10.1.3. Dinuclear Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245 10.1.4. Trinuclear and Larger Clusters . . . . . . . . . . . . . . . . . . . . . 247

10.2. Insertion and Migration Reactions . . . . . . . . . . . . . . . . . . . . . . . . . 251 10.2.1. Carbon Monoxide Insertion . . . . . . . . . . . . . . . . . . . . . . . 252 10.2.2. Alkene and Alkyne Insertions . . . . . . . . . . . . . . . . . . . . . . 254 10.2.3. Other Insertions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258

Chapter ll. Metal-Alkyl and Metal-Hydride Bond Formation and Fission; Oxidative Addition and Reductive Elimination

R. D. Pike

11.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261 11.2. Dihydrogen Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262

11.2.1. Criteria for Characterization . . . . . . . . . . . . . . . . . . . . . . . 262 11.2.2. Bonding . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . 263 11.2.3. Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264 11.2.4. New Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266

11.3. Metal-Hydride Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267 11.4. C- H Bond Activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269

11.4.1. Unactivated C-H Bonds . . . . . . . . . . . . . . . . . . . . . . . . . 270 11.4.2. Activated C-H Bonds............................ 271 11.4.3. Intramolecular C-H Bonds . . . . . . . . . . . . . . . . . . . . . . . 274

11.5. Reductive Elimination Forming Carbon-Carbon Bonds . . . . . . . 278 11.6. Oxidative Addition and Reductive Elimination of Alkyl Halides 279 11.7. Oxidative Addition and Reductive Elimination Involving

Two Metal Centers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280

Chapter 12. Reactivity of Coordinated Ligands

R. W. Hay, E. C. Constable, and L.A. P. Kane-Maguire

12.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283 12.2. Cobalt Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283

Contents XV

12.2.1. Phosphates and Phosphate Esters . . . . . . . . . . . . . . . . . . 283 12.2.2. Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285 12.2.3. Nitriles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285 12.2.4. Bromination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286 12.2.5. Amino Acid Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . 286

12.3. Other Metal Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288 12.3.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288 12.3.2. Nitriles and Related Ligands . . . . . . . . . . . . . . . . . . . . . . . 289

· 12.3.3. Carbonyls and Imines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290 12.3.4. Electrophilic Attack at Coordinated Nitrogen

and Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293 12.3.5. Reactions of Coordinated Phosphorus Compounds . . . . 296 12.3.6. Reactions of Coordinated Sulfur Ligands . . . . . . . . . . . . 298 12.3.7. Reactions of Coordinated Heterocyclic Ligands . . . . . . . 300 12.3.8. Oxygen Atom Transfer and Ligand Oxidation . . . . . . . . 302

12.4. Organometallic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 307 12.4.1. Reactions with Nucleophiles . . . . . . . . . . . . . . . . . . . . . . . 307 12.4.2. Reactions with Electrophiles . . . . . . . . . . . . . . . . . . . . . . . 317

Chapter 13. Rearrangements, Intramolecular Exchanges, and lsomerizations of Organometallic Compounds

K. G. Orrell

13.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321 13.2. Mononuclear Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321

13.2.1. Isomerizations and Changes in Bonding Type . . . . . . . . 321 13.2.2. Ligand Rotations about Metal-Ligand Bonds . . . . . . . . 324 13.2.3. Migrations of Metal Atoms between Different

Ligand Sites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330 13.2.4. Agostic Bonding and Hydrogen Atom Migrations . . . . . 333 13.2.5. Internal Ligand Rearrangements . . . . . . . . . . . . . . . . . . . . 336

13.3. Dinuclear Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348 13.3.1. Restricted Rotations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348 13.3.2. Carbonyl Ligand Migrations . . . . . . . . . . . . . . . . . . . . . . . 349 13.3.3. Migrations of Other Ligands between Metal Atoms . . . 350 13.3.4. Isomeric Exchanges..... . . . . . . . . . . . . . . . . . . . . . . . . . . 351 13.3.5. Other Exchange Processes . . . . . . . . . . . . . . . . . . . . . . . . . 352

13.4. Metal Cluster Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353 13.4.1. Rearrangements Involving the Relative Motion of

Metal Atoms in a Cluster . . . . . . . . . . . . . . . . . . . . . . . . . . 353 13.4.2. Carbonyl Exchanges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355 13.4.3. Other Exchange Processes . . . . . . . . . . . . . . . . . . . . . . . . . 358

xvi

Chapter 14. Homogeneous Catalysis of Organic Reactions by Transition Metal Complexes

M. Bochmann

Contents

14.1. General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363 14.2. Isomerization and Hydrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . 364 14.3. C- H Activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 369 14.4. Hydrosilylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 372 14.5. Nucleophilic Additions to C=C and C=C . . . . . . . . . . . . . . . . . . 375 14.6. Dimerizations and Oligomerizations . . . . . . . . . . . . . . . . . . . . . . . . 377 14.7. Olefin Metathesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380 14.8. Alkene Polymerizations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381 14.9. Carbonylations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388 14.10. C-C Coupling Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394

Part IV. Compilations of Numerical Data

Chapter 15. Volumes of Activation for Inorganic and Organometallic Reactions: A Tabulated Compilation

A. Neubrand and R. van Eldik

15.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399 15.2. Data in Tabular Form . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 400

References.................................................... 419

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 481