Mechanisms of Inorganic and Organometallic Reactions: Volume 2

457 Pages·1984·9.58 MB·English

by  M. V. Twigg (auth.), M. V. Twigg (eds.)

Volume 2
Mechanisms of Inorganic
and Organometallic Reactions
A Continuation Order Plan is available for this series. A continuation order will
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publisher.
Volume 2
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.
1. Chemical reactions. 2. Chemistry, Inorganic. 2. Organometallic compounds. I.
Twigg, M. V.
QD501.M426 1983 541.3'9 83-2140
ISBN-13: 978-1-4612-9659-1 e-ISBN-13: 978-1-4613-2663-2
DOl: 10.1007/978-1-4613-2663-2
© 1984 Plenum Press, New York
Softcover reprint of the hardcover 1st edition 1984
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. f. Burgess Chemistry Department, The University,
Leicester LEl 7RH, U.K.
Dr. R. D. Cannon Chemistry Department, University of East Anglia,
University Plain, Norwich NR47Tl, U.K.
Dr. R. f. Cross Department of Chemistry, The University,
Glasgow G12 8QQ, Scotland, U.K.
Dr. A. f. Deeming Chemistry Department, University College London,
20 Gordon Street, London WCIH OAl, u.K.
Dr. M. Green Chemistry Department, The University, York,
North Yorkshire, YOl 5DD, U.K.
Dr. D. N. Hague Chemical Laboratory, The University, Canterbury,
Kent CT2 7NH, U.K.
Dr. R. W. Hay Department of Chemistry, University of Stirling,
Stirling FK9 4LA, Scotland, U.K.
Dr. M. N. Hughes Chemistry Department, Queen Elizabeth College,
University of London, London W8 7 AH, U.K.
Dr. L. A. P. Kane-Maguire Chemistry Department, Wollongong
University, P.O. Box 1144, Wollongong, N.S.W. 2500, Australia
Dr. A. G. Lappin Chemistry Department, University of Notre
Dame, Notre Dame, Indiana 46556, U.S.A.
vi Contributors
Dr. P. Moore Department of Chemistry and Molecular Sciences,
University of Warwick, Coventry CV47AL, U.K.
Dr. D. A. Sweigart Department of Chemistry, Brown University,
Providence, Rhode Island 02912, U.S.A.
Dr. C. White Department of Chemistry, The University of Sheffield,
Sheffield S3 7HF, U.K.
Preface
This series provides a continuing critical review of the literature concerned
with mechanistic aspects of inorganic and organometallic reactions in solu
tion, with coverage over the whole area being complete in each volume.
The format of this second volume is very similar to that of the first, with
material arranged according to reaction type and compound type along
generally accepted lines. Papers discussed are selected on the basis of
relevance to the elucidation of reaction mechanisms but may also include
results of a nonkinetic nature, such as stereochemical studies and product
ratios, when useful mechanistic information can be deduced.
In this volume extra space has been given to areas concerned with
electron transfer processes and substitution reactions of inert complexes,
and to improve convenience for the reader the text has been further divided
to form three additional chapters. Electron transfer processes are discussed
in three chapters: "General and Theoretical," "Reactions between Two
Complexes," and "Metal-Ligand Redox Reactions," while six chapters are
concerned with substitution and related reactions. Here reactions of inert
chromium and cobalt complexes are discussed in separate chapters.
The period of literature coverage is January 1981 through June 1982
inclusive and in a few instances, where delays in delivery of journals have
been encountered, the issues not covered will be included in the next volume.
Similarly, some 1980 references that were not available for inclusion in the
previous volume are discussed here. Numerical results are usually reported
in units used by the original authors, except where data from different
papers are compared and conversion to common units is necessary.
This series was established as a result of demand from members of the
Inorganic Mechanisms Discussion Group (UK), and their continuing sup
port is appreciated by the contributors, and by others involved in producing
the series. Comments and suggestions regarding this and future volumes
will be welcomed.
vii
Contents
Part 1. Electron Transfer Reactions
Chapter 1. Electron Transfer: General and Theoretical
R. D. Cannon
1.1. Reviews .............. . 3
1.2. The Marcus-Hush Model . . . . . . . . 3
1.3. Quantum Effects: (1) The "Normal" Region 6
1.4. Quantum Effects: (2) The "Inverted" Region 9
1.5. Optical and Thermal Electron Transfer 12
1.6. Mixed-Valence Complexes 16
1. 7. Electron Transfer in the Solid State 21
Chapter 2. Redox Reactions between Metal Complexes
A. G. Lappin
2.1. Introduction ... . 23
2.2. Titanium(III) ... . 23
2.3. Chromium(II) and (III) 36
2.4. Iron(II) . . . . . 37
2.5. Cobalt(II) 42
2.6. Nickel(II) and (III) 43
2.7. Copper(I) and (II) 44
2.8. Molybdenum(IV) and (V) 45
2.9. Ruthenium(II) 46
2.10. [*Ru(bipyhf+ .... 47
ix
x Contents
2.11. Europium(II) ..... 48
2.12. Miscellaneous Reactions 49
2.13. Metalloprotein Studies . 49
Chapter 3. Metal-Ligand Redox Reactions
A. G. Lappin
3.1. Introduction .... 53
3.2. Ascorbic Acid H2A 53
3.3. Quinols and Catechols 55
3.4. Halogens and Pseudohalogens 56
3.5. Thiols, Sulfur, Selenium, and Tellurium Compounds 59
3.6. Amines ......... . 61
3.7. Carbonyls and Carboxylic Acids 62
3.8. Alcohols and Diols ... . 64
3.9. Alkenes and Alkyls .... . 65
3.10. Nitrogen and Nitrogen Oxides . 66
3.11. Peroxydisulfate and Peroxymonosulfate 68
3.12. Oxyhalogen Anions 70
3.13. Reactions of O2 and H20 2 71
3.14. Miscellaneous Reactions 74
Part 2. Substitution and Related Reactions
Chapter 4. Reactions of Compounds of the Nonmetallic Elements
M. N. Hughes
4.1. Introduction 79
4.2. Boron 79
4.3. Silicon 80
4.3.1. Silicon Radicals 80
4.3.2. Base Hydrolysis 81
4.3.3. Various Substitutions, Isomerizations, and
Redistributions .......... . 81
4.3.4. Reactions of I3-Substituted Organosilicon
Compounds ............ . 83
4.3.5. Aqueous Solutions of Silicates 84
4.4. Nitrogen ......... . 84
4.4.1. Nitric Acid and Nitration 84
4.4.2. Nitrogen Dioxide . . . 86
Contents xi
4.4.3. Nitrous Acid and Nitrosation 86
4.4.4. Trioxodinitrate and Nitrogen Monoxide 89
4.4.5. Hyponitrite 90
4.4.6. Dinitrogen Complexes 90
4.4.7. Azide 90
4.4.8. Nitroamine and Hydroxylamine 91
4.4.9. Hydrazine 93
4.5. Phosphorus and Arsenic 93
4.5.1. Phosphorus(V) Compounds 93
4.5.2. Phosphorus(III) Compounds 94
4.5.3. Phosphorus(l) Compounds 95
4.5.4. Arsenic Compounds 95
4.6. Oxygen 95
4.7. Sulfur 97
4.7.1. Oxidation with Peroxo Acids of Sulfur 97
4.7.2. Reactions of Oxo Acids of Sulfur 98
4.7.3. Decomposition of a Sulfur Nitroso Compound
(S-Nitrosothiouronium Ion) 98
4.8. Selenium and Tellurium 99
4.8.1. Oxidation of Selenium(IV) 99
4.8.2. Tellurium Compounds 99
4.9. Halogens 99
4.9.1. Fluoroxysulfate 99
4.9.2. Chlorine Compounds 100
4.9.3. Bromine Dioxide 100
4.9.4. Iodine Compounds 101
4.9.5. Oscillating Reactions 101
4.10. Xenon 103
Chapter 5. Substitution Reactions of Inert Metal Complexes
Coordination Numbers 4 and 5
R. J. Cross
5.1. Introduction .............. . 105
5.2. Substitution at Square-Planar Palladium(II) and
Platinum(II) .............. . 106
5.2.1. Palladium(II) Complexes 106
5.2.2. Platinum(II) Complexes . . 108
5.2.3. Electrophilic Substitutions . 111
5.3. Ring Opening and Closing Reactions 113
5.3.1. Palladium(II) Complexes 113
5.3.2. Platinum(II) Complexes .. 115