Table Of ContentA Specialist Periodical Report
Inorganic Reaction Mechanisms
Volume 6
A Review of the Literature Published between
July 1976 and December 1977
Senior Reporter
A. McAuley, Department of Chemistry, University of Victoria,
British Columbia, Canada
Reporters
J. Burgess, University of feicester
R. D. Cannon, University of East Anglia
J. L. Davidson, Heriof- Watf University, Edinburgh
D. N. Hague, University ofKent
A. G. Lappin, University of Glasgow
W. E. Lindsell, Heriot- Watt University, Edinburgh
P. Moore, University of Warwick
G. Stedman, University College of Swansea
The Chemical Society
Burlington House, London WiV OBN
British Library Cataloguing in Publication Data
Inorganic reaction mechanisms.-
(Chemical Society, Specialist periodical reports),
Vol. 6
1. Chemistry, Inorganic
2. Chemical reactions
I. McAuley, Alexander 11. Series
541’.39 QD151.2 73-642977
ISBN 0-85186-305-1
ISSN 0305-8255
Copyright 0 1979
The Chemical Society
All Rights Reserved
No part of this book may be reproduced or transmitted
in any form or by any means - graphic, electronic,
including photocopying, recording, taping or
information storage and retrieval systems - without
written permission from The Chemical Society
Printed in Great Britain by Adlard & Son Ltd, Bartholomew Press, Dorking
Fore word
The format, coverage, and approach to this Sixth Volume dealing with Inorganic
Reaction Mechanisms are similar to those for the previous volumes in this series. In
view of the enormous scope for selection of materials, we have chosen (with an
eye to cost and volume size) to concentrate on papers where kinetics and mechanisms
in solution are the subjects of principal interest. Inevitably, in some papers where
there is reference to mechanisms the treatment is somewhat more cursory with a
consequent loss of subtlety. We hope, however, that any resultant oversimplification
or misrepresentation is minimal. Review articles cited are those which should be
accessible to the great majority of readers. Additional bibliography has been pro-
vided in the organometallic sections.
The period of coverage is from June 1976 to December 1977. The boundaries at
both ends are somewhat vague since not all libraries have journal issues available
at the same time. Care has been taken, however, to ensure that an overlap with
Volume 5 is maintained in all areas. Where material has been derived from Chemical
Abstracts rather than the original source a Chem. Abs. citation has been included in
the reference quoted. References to the Russian literature derived from this source
quote the page number of the original article whereas those giving the title of the
English translation quote the page number of the translation.
As in previous volumes, kinetic data are reported in the form and units used in
the original articles (Ea,l og A or AH* and AS*). Some conversions have been made
both in the text and in the tables where comparisons are required.
The Reporters are grateful to many of their colleagues for helpful comments and
for the critical reading of many of the chapters in this volume.
A. MCAULEY
Cont ents
~~
Part I Electron Transfer Processes
Introduction 3
Chapter 1 Reactions Between Two Metal Complexes 5
By R. D. Cannon
1 General and Theoretical 5
Non-adiabaticity 5
Tunnelling 9
The Inverted Region 10
The Cross Relation 11
Other Theoretical Work 12
Related Areas 14
2 Intramolecular Electron Transfer 15
Precursor Complexes of Known Structure 15
Labile Dinuclear Intermediates- Direct Observation 16
Labile Dinuclear Intermediates- Indirect Evidence 18
Optical Electron Transfer 19
Mixed-valence Compounds 20
3 Intermolecular Electron Transfer 22
Inner- and Outer-sphere Mechanisms 22
Organic Bridging Ligands 24
Excited States 31
Non-complement a r y Reacti ons 32
Chapter 2 Metal Ion-Ligand Redox Reactions 69
By A. G. Lappin and A. McAuley
1 Iron(m) 69
2 CObalt(III) 78
3 Chromium(w) 82
4 Manganese(m) and Manganese(vni) 84
5 Copper(I1) and Copper (111) 85
vi Contents
6 Cerium(1v) 90
7 ThalliumOzI) 92
8 Nickel(1n) 94
9 Peroxodisulsphate 95
10 Peroxodiphosph a t e 97
11 Other Redox Reactions 98
Platinum(1v) 98
Octacyanometallate(v) Ions 98
Actinides 99
Gold (111) 100
Hexachloroirida te(rv) 100
Periodate and Iodate 101
Pal ladium(r1) Complexes 102
Vanadium(v) 102
Osmium(v1Ir) 102
Ruthenium(1v) 103
12 Metal-ion Reductions 103
13 Pulse Radiolysis 109
Chapter 3 Reactions involving Oxygen and Hydrogen Peroxide 115
By A. McAuley
1 Cobalt Complexes 115
2 Iron(u) Complexes 117
3 Other Metal Complexes 118
4 Hydrogen Peroxide Reactions 121
___
Part /I Substitution and Related Reactions
Chapter 1 Non-metallic Elements 129
By G. Stedman
1 Group 111 129
Boron 129
Tetrahedral Anions and Related Species 129
Boron-Hydrogen Compounds 130
Boron-Oxygen Compounds 130
Contents vii
Aluminium 130
Gallium 131
Indium 131
Thallium 132
2 GroupIV 132
Carbon 132
Silicon 133
Germanium 137
Tin 137
Lead 138
3 Group V 139
Nitrogen 139
Phosphorus 142
Oxoanions and Related Species 142
Phosphorus-Oxygen-Nitrogen Compounds 144
Phosphazenes 144
Miscellaneous Compounds 145
Intramolecular Processes 146
Arsenic 147
Antimony 147
Bismuth 147
4 GroupVI 148
Sulphur 148
Selenium 149
Tellurium 149
5 GroupVII 150
Fluorine 150
Chlorine 150
Bromine 151
Iodine 151
Astatine 151
6 Group VIII 151
Xenon 151
Chapter 2 Inert Metal Complexes: Co-ordination Numbers Four
and Five 153
By J. Burgess
1 Square-planar Complexes 153
Plat inum(I1) 155
Aquation, Solvolysis, and Anation 155
viii Contents
Ligand Exchange 156
Entering Groups 156
Ring Closure 156
Ring Opening 157
Isomerization, Symmetrization, and Inversion 158
Effects of Non-leaving Ligands 160
Photochemistry 161
Reactions of Co-ordinated Ligands 161
Palladium(I1) 162
Solvolysis and Anation 162
Substitution 162
Isomerization and Inversion 163
Polynuclear Complexes 163
Reactions of Co-ordinated Ligands 164
Gold@) 164
Substitution 164
Isomerization 165
Redox and Substitution 165
Nickel(@ 165
Copper(d 166
2 Tetrahedral Complexes 167
sp-Block Metals 1 67
Transition Metals : Nickel(@ Complexes 168
Transition Metals : Oxoanions and Polynuclear Species 168
3 Five-co-ordinate Complexes 171
Chapter 3 Inert Metal Complexes: Co-ordination Number Six
and Higher 1 74
By P. Moore
1 Introduction 174
2 Aquation: Cobalt(n1) Complexes 183
Unidentate Leaving Groups 183
Multidentate Leaving Groups 186
Effects of Non-leaving Ligands 187
[C~(en),xY]~C+o mplexes 187
[Co(LL),(L)X]n+ and [CO(LLL)(LL)X]~+C omplexes 189
[Co(LLLL) (L)X]n+ and [Co(LLLL)(LL)ln+ Complexes 189
Dioximato-complexes 193
Bridged Dicobalt Complexes 196
Solvent Variation 198
Catalysed Aquation 198
Photochemistry 1 99
