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Volume 1
Mechanisms of Inorganic and Organometallic Reactions
Edited by
M. V. Twigg Imperial Chemical Industries P. L. C. Billingham, United Kingdom
PLENUM PRESS • NEW YORK AND LONDON
Library of Congress Cataloging in Publication Data
Main entry under title:
Mechanisms of inorganic and organometallic reactions. Includes bibliographical references and index. I. Chemical reactions. 2. Chemistry, Inorganic. 2. Organometallic compounds. I.
Twigg, M .. V. QD50l.M426 1983 541.3'9 83-2140
ISBN 978-1-4615-7412-5 ISBN 978-1-4615-7410-1 (eBook) DOI 10.1007/978-1-4615-7410-1
© 1983 Plenum Press, New York Sof'tcover reprint of the hardcover I st edition 1983
A Division of Plenum Publishing Corporation 233 Spring Street, New York, N.Y. 10013
All 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
Dr. 1. Burgess ter, U.K.
Chemistry Department, The University of Leicester, Leices-
Dr. 1. Coe Chemistry Department, Kings College, London University, The Strand, London WC2, U.K.
Dr. I.M. Davidson Dept. of Chemical Engineering, University of Edin-burgh, Kings Building, Edinburgh EH9 3JL, Scotland, U.K.
Dr. A.l. Deeming Chemistry Department, University College London, 20 Gordon Street, London WCIH OAJ, U.K.
Dr. M. Green Chemistry Department, The University of York, York, North Yorkshire, U.K.
Dr. D. Hague Chemical Laboratory, The University of Kent, Canterbury, Kent, U.K.
v
vi Contributors
Dr. M.N. Hughes Chemistry Department, Queen Elizabeth College, Uni-versity of London, London W8 7AH, U.K.
Dr. L.A.P. Kane-Maguire Chemistry Department, University College, Car-diff CFl IXL, Wales, U.K.
* Dr. A.G. Lappin Chemistry Department, University of Glasgow, Glasgow, Scotland, U.K.
Professor A. McAuley Department of Chemistry, University of Victoria, British Columbia, Canada
Dr. P. Moore Department of Chemistry and Molecular Sciences, University of Warwick, Coventry CV4 7AL, U.K.
*Presently: Department of Chemistry . University of Notre Dame. Notre Dame, Indiana46556, U.S.A.
Preface
During recent years a high level of interest has been maintained in the kinetics and mechanisms of inorganic compounds in solution, and there has also been a notable upsurge of literature concerned with reaction mechanisms of organotransition metal compounds. The reviews of the primary literature previously provided by "Inorganic Reaction Mechanisms" (Royal Society of Chemistry) and "Reaction Mechanisms in Inorganic Chemistry" in "MTP International Reviews of Science" (Butterworths) continue to be of considerable value to those concerned with mechanistic studies, and it is unfortunate they are no longer published.
The objective of the present series is to provide a continuing critical review of literature dealing with mechanisms of inorganic and organometallic reactions in solution. The scope of potentially relevant work is very large, particularly in the field of organotransition metal chemistry, and papers for inclusion have been chosen that specifically probe mechanistic aspects, rather than those of a preparative nature. This volume covers the literature published during the period July 1979 to December 1980 inclusive. Material is arranged basically by type of reaction and type of compound along generally accepted lines. Numerical data are usually reported in the units used by the original authors, though the units of some results have been converted in order to make comparisons.
Many people, most of whom are members of the Inorganic Mechanisms Discussion Group (UK), were involved in establishing this series. Their help is gratefully acknowledged, as is the enthusiastic and prompt way in which contributions were prepared. Comments on this and future volumes will be welcomed.
vii
Contents
Part 1. Electron Transfer Reactions
Chapter 1. General Redox Processes and Reactions between Two Complexes
A.G. Lappin
1.1. Introduction............................................ 3 1.2. General Background. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2. 1. General and Theoretical . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 1.2.2. Theoretical Developments ......................... 4 1.2.3. Optical Electron Transfer. . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.3. Reaction Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 11 1.3.1. Inner-Sphere and Outer-Sphere Reactions. . . . . . . . . . . .. 11 1.3.2. Solvent Effects in Electron Transfer Reactions. . . . . . . .. 30
1.4. Excited State Electron Transfer . . . . . . . . . . . . . . . . . . . . . . . . . . .. 31 1.5. Stereoselectivity in Electron Transfer. . . . . . . . . . . . . . . . . . . . . . .. 34 1.6. Metalloprotein Redox Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . .. 34
Chapter 2. Metal-lon-Ligand Redox Reactions
A. McAuley
2.1. Introduction............................................ 37 2.2. Metal Complexes with Inorganic Substrates. . . . . . . . . . . . . . . . .. 38
2.2.1. Reactions of Hydrazine and Hydroxylamine. . . . . . . . . .. 38 2.2.2. Reactions of Nitrate and Nitrite. . . . . . . . . . . . . . . . . . . .. 39
ix
x Contents
2.2.3. Reactions of Thiocyanate. . . . . . . . . . . . . . . . . . . . . . . . .. 40 2.2.4. Reactions of Dithionite and Thiosulfate .............. 40 2.2.5. Reactions of Iodide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 41 2.2.6. Other Reductants ............................... " 42
2.3. Oxidation of Organic Substrates by Metal Ion Complexes. . . . . .. 43 2.3.1. Chromium(VI)................................... 44 2.3.2. Vanadium(V).................................... 46 2.3.3. Manganese(III) and Manganese(VII) . . . . . . . . . . . . . . . .. 46 2.3.4. Iron(III)........................................ 48 2.3.5. Thallium(III).................................... 49 2.3.6. Iridium(IV)..................................... 49 2.3.7. Cerium(IV)..................................... 50 2.3.8. Cobalt(III)...................................... 51 2.3.9. Bromate........................................ 52 2.3.10. Other Oxidizing Agents. . . . . . . . . . . . . . . . . . . . . . . . . .. 53
2.4. Oxidation of Metal Ion Complexes ......................... 54 2.4.1. Iron(lI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 54 2.4.2. Chromium(II)................................... 56 2.4.3. Vanadium(II) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 57 2.4.4. Coba1t(II) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 58 2.4.5. Other Reductants. ................................ 59
2.5. Intramolecular Electron Transfer. . . . . . . . . . . . . . . . . . . . . . . . . .. 59
Part 2. Substitution and Related Reactions
Chapter 3. Reactions of Compounds of the Nonmetallic Elements
M.N. Hughes
3.1 . Introduction............................................ 65 3.2. Boron................................................. 65 3.3. Group IV Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 68
3.3.1. Carbon......................................... 68 3.3.2. Silicon......................................... 69 3.3.3. Germanium..................................... 70
3.4. Group V Elements. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 71 3.4.1. Nitrogen........................................ 71 3.4.2. Phosphorus..................................... 76 3.4.3. Arsenic........................................ 80 3.4.4. Antimony....................................... 80
Contents xi
3.5. Group VI Elements. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 80 3.5.1. Oxygen........................................ 80 3.5.2. Sulfur .......................................... 81 3.5.3. Selenium....................................... 84 3.5.4. Tellurium....................................... 84
3.6. Group VII Elements. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 84 3.6.1. Fluorine........................................ 84 3.6.2. Chlorine........................................ 85 3.6.3. Bromine........................................ 85 3.6.4. Iodine.......................................... 86
Chapter 4. Substitution Reactions of Inert Metal ComplexesCoordination Numbers 4 and 5
J.S. Coe
4.1. Introduction............................................ 87 4.2. Square-Planar Complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 88
4.2.1. Platinum(II)..................................... 88 4.2.2. Palladium(II).................................... 93 4.2.3. Nickel(II) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 95 4.2.4. Gold(III)....................................... 98 4.2.5. Miscellaneous................................... 99 4.2.6. Isomerization .................................... 100
4.3. Tetrahedral Complexes ................................... 101 4.4. Five-Coordinate Complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 101
Chapter 5. Substitution Reactions of Inert Metal ComplexesCoordination Numbers 6 and Above
J. Burgess and P. Moore
5. 1. Introduction............................................ 103 5.2. Chromium ............................................. 105
5.2.1. Introduction ..................................... 105 5.2.2. Aquation and Solvolysis of Chromium(III) Complexes.. 105 5.2.3. Formation of Chromium(III) Complexes. . . . . . . . . . . . .. 117 5.2.4. Chromium(III) Photochemistry ..................... 124 5.2.5. Isomerization and Racemization Reactions. . . . . . . . . . .. 125 5.2.6. Base Hydrolysis ................................. 126 5.2.7. Solids .......................................... 126 5.2.8. Other Chromium Oxidation States. . . . . . . . . . . . . . . . . .. 127
xii Contents
5.3. Group VII Elements ..................................... 127 5.3.1. Technetium ..................................... 127 5.3.2. Rhenium....................................... 128
5.4. Iron ................................................... 128 5.4.1. Pentacyanoferrate(II) Complexes. . . . . . . . . . . . . . . . . . .. 129 5.4.2. Diimine Complexes .............................. 133 5.4.3. Other Low-Spin Iron(II) Complexes. . . . . . . . . . . . . . . .. 139 5.4.4. Iron(III) Complexes .............................. 140
5.5. Ruthenium ............................................. 141 5.5.1. Ruthenium(II) ................................... 141 5.5.2. Ruthenium (III) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 143 5.5.3. Ruthenium(IV) .................................. 145
5.6. Osmium ............................................... 145 5.7. Cobalt(III)............................................. 146
5.7.1. Aquation and Solvolysis. . . . . . . . . . . . . . . . . . . . . . . . . .. 146 5.7.2. Base Hydrolysis and Base Solvolysis ................ 154 5.7.3. CatalyzedAquation ............................... 157 5.7.4. Formation...................................... 160 5.7.5. Solvent and Ligand Exchange ...................... 164 5.7.6. Racemization and Isomerization .................... 167 5.7.7. Carbonate and Sulfite Complexes ................... 170 5.7.8. Bis(glyoximato) Complexes ........................ 172 5.7.9. f.L-Dicobalt(III) Complexes. . . . . . . . . . . . . . . . . . . . . . . .. 174 5.7.10. Photochemistry .................................. 176 5.7.11. Reactions of Coordinated Ligands. . . . . . . . . . . . . . . . . .. 177
5.8. Rhodium(III)........................................... 179 5.8.1. Aquation ....................................... 180 5.8.2. Base Hydrolysis ................................. 180 5.8.3. Catalyzed Aquation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 181 5.8.4. Formation ...................................... 181 5.8.5. Solvent and Ligand Exchange. . . . . . . . . . . . . . . . . . . . .. 182 5.8.6. Ring Opening and Closing. . . . . . . . . . . . . . . . . . . . . . . .. 182 5.8.7. Isomerization.................................... 183 5.8.8. Carbonate and Sulfite Complexes ................... 183 5.8.9. Bis(glyoximato) Complexes ........................ 186 5.8.10. Photochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 186
5.9. Iridium ................................................ 188 5.9. 1. Iridium(III)..................................... 188 5.9.2. Iridium(IV) ..................................... 190
5.10. Platinum(lV) ........................................... 190 5.10.1. General ........................................ 190 5.10.2. Inversion at Coordinated Sulfur and Selenium ......... 190
Contents xiii
Chapter 6. Substitution Reactions of Labile Metal Complexes
D.N. Hague
6.1. Complex Formation Involving Unsubstituted Metal Ions with Unidentate Ligands and Solvent Exchange . . . . . . . . . . . . . . . . . .. 193 6.1.1. Univalent Ions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 193 6.1.2. Bivalent Ions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 193 6.1.3. Ions of Valency 3 and Higher. . . . . . . . . . . . . . . . . . . . .. 195
6.2. Complex Formation Involving Unsubstituted Metal Ions and Multidentate Ligands. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 197 6.2.1. Univalent Ions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 197 6.2.2. Bivalent Ions .................................... 198 6.2.3. Ions of Valency 3 and Higher ...................... 202
6.3. The Effects of Bound Ligands ............................. 203 6.3 . 1. Reactions in Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 203 6.3.2. Reactions in Nonaqueous Solvents .................. 207
Part 3. Reactions of Organometallic Compounds
Chapter 7. Metal-Alkyl Bond Fission and Formation
M. Green
7.1. Introduction............................................ 211 7.2. Metal-Alkyl Bond Fission ................ . . . . . . . . . . . . . . .. 211 7.3. Miscellaneous Thermal Decompositions ..................... 216 7.4. Metal-Alkyl Bond Formation .............................. 217 7.5. Transalkylation ......................................... 219
Chapter 8. Substitution, Oxidative Addition-Reductive Elimination, and Migration-Insertion Reactions
M. Green
8.1. Introduction ............................................ 223 8.2. Substitution Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 223
8.2.1. Reactions Involving Carbonyls or Carbon Monoxide .... 223 8.2.2. Reactions Involving Di- or Multihapto Ligands ........ 228
xiv Contents
8.3. Oxidative Addition and Reductive Elimination ................ 231 8.4. Migration-Insertion Reactions ............................. 243
Chapter 9. Rearrangements, Intramolecular Exchanges, and Isomerization of Organometallic Compounds
A.J. Deeming
9.1. Mononuclear Compounds ............................... " 249 9.1.1. Isomerizations and Intramolecular Exchanges. . . . . . . . .. 249 9.1.2. Simple Ligand Rotation at a Metal Center ............ 251 9.1. 3. Ligand Motion Involving Changes in Hapiticity. . . . . . .. 256 9.1.4. Metal Migration between Different Ligand Sites ....... 259 9.1.5. Hydrogen Migrations Involving Hydrogen Bound to
Carbon .......................................... 260 9.1.6. Alkyl Migration Reactions ......................... 263 9. 1.7. Intraligand Rotations and Rearrangements ............ 263
9.2. Dinuclear Compounds .................................... 264 9.2.1. Migration of CO and Related Ligands ............... 264 9.2.2. Hydrogen Migration Reactions ..................... 265 9.2.3. Motion Involving Bridging Organic Ligands .......... 266 9.2.4. Rotation about Metal-Metal Bonds .................. 268
9.3. Cluster Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 268 9.3.1. Fluxional Metal Frameworks . . . . . . . . . . . . . . . . . . . . . .. 268 9.3.2. Migration of CO and Related Ligands ............... 268 9.3.3. Hydrogen Migration Reactions ..................... 270 9.3.4. Motion Involving Bridging Organic Ligands .......... 270
Chapter 10. Reactivity of Coordinated Hydrocarbons
L.A.P. Kane-Maguire
10.1. Introduction ............................................ 273 10.2. Nucleophilic Addition and Substitution. . . . . . . . . . . . . . . . . . . . .. 273
10.2.1. a-Bonded Hydrocarbons. . . . . . . . . . . . . . . . . . . . . . . . . .. 273 10.2.2. 1T-Bonded Hydrocarbons .......................... 276 10.2.3. Reactions at Side Chains and Exocyclic Carbocations ... 290 10.2.4. Attack at Carbonyl Ligands ........................ 292
10.3. Electrophilic Attack ...................................... 293
Contents
Chapter 11. Homogeneous Catalysis of Organic Reactions by Complexes of Metal Ions
1.M. Davidson
xv
11.1. Introduction............................................ 295 11. 1.1. Scope of the Review. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 295 11.1.2. Elementary Steps in Homogeneous Catalysis .......... 295
11.2. Reactions Catalyzed by Carbene Complexes .................. 296 11.2.1. Alkene Metathesis ................................ 296 11.2.2. Ring-Opening Polymerization by Metallocarbene
Complexes ...................................... 301 11.3. Hydrogenation .......................................... 301
11. 3. 1. Introduction..................................... 301 11.3.2. Hydrogenation of Alkenes ......................... 302 11.3.3. Asymmetric Hydrogenation ........................ 303 11.3.4. Hydrogenation of Aromatic Hydrocarbons ............ 306 11. 3.5. Hydrogen Transfer Hydrogenation. . . . . . . . . . . . . . . . . .. 307
11.4. Reactions of Carbon Monoxide .. . . . . . . . . . . . . . . . . . . . . . . . . .. 308 11.4.1. Hydroformylation ................................ 308 11.4.2. Carbonylation of Alcohols ......................... 308 11.4.3. The Homogeneous Water Gas Shift Reaction (WGSR) .. 311
11.5. Oxidation .............................................. 314
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 317
Author Index . .......................................... 351
General Subject Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 367