Table Of ContentORGANOMETALLIC COMPOUNDS
VOLUME ONE
THE MAIN GROUP ELEMENTS
PART TWO
Groups IV and V
ORGANOMETALLIC COMPOUNDS
FOURTH EDITION
G. E. Coates, B. J. Aylett, M. L. H. Green,
D. M. P. Mingos, K. Wade
VOLUME ONE
THE MAIN GROUP ELEMENTS
PART ONE
Groups I-III
G. E. COATES and K. WADE
PART TWO
Groups IV and V
B. J. AYLETT
VOLUME TWO
THE TRANSITION ELEMENTS
M. L. H. GREEN and D. M. P. MINGOS
ORGANOMETALLIC
COMPOUNDS
FOURTH EDITION
VOLUME ONE
THE MAIN GROUP ELEMENTS
PART TWO
Groups IV and V
B. J. AYLETT
Professor of Chemistry, Westfield College, London
LONDON
CHAPMAN AND HALL
A Halsted Press Book
John Wiley & Sons, New York
First published 1956
by Methuen & Co Ltd
Second Edition 1960
Third Edition published in two volumes
Volume One published 1967, Volume Two published 1968
Reprint 1972 published by Chapman and Hall Ltd
Fourth Edition 1979
published by Chapman and Hall Ltd, 11 New Fetter Lane London EC4P 4EE
Typeset by John Wright & Sons Ltd, at the Stonebridge Press, Bristol
and printed in Great Britain by William Clowes & Sons Ltd., London and Beccles
Volume I Part 2 © 1979 B. J. Aylett
Softcover reprint of the hardcover 1s t edition 1979
ISBN-13: 978-94-009-5731-2 e-ISBN-13: 978-94-009-5729-9
DOI: 10.1007/978-94-009-5729-9
All rights reserved. No part of this book
may be reprinted, or reproduced or utilized
in any form or by any electronic, meehanical or
other means, now known or hereafter invented,
including photocopying and reeording, or in any
information storage and retrieval system, without
permission in writing from the publisher.
Distributed in the USA by Halsted Press,
A Division ofJ ohn Wiley & Sons, Ine., New York
British Library Cataloguing in Publication Data
Organometallic compounds.-4th ed.
Vol. 1: Main group elements. Part 2: Groups IV and V
1. Organometallic compounds
1. Aylett, B J II. Coates, Geoffrey, Edward
547'.05 QD411 79-42877
New York, USA Halsted Press 0 470-26874-3
PREFACE TO THE
FOURTH EDITION
VOLUME ONE, PART TWO
The first edition of this book appeared as a slim monograph in 1956, the
second as a more substantial text in 1960, and the third as two considerable
volumes in 1967-1968. It is a measure of the development of academic and
industrial interest in organometallic chemistry over the last decade that the
volume concerned with Main Group elements in the fourth edition must be
divided into two parts. This part, the first to appear, deals with Groups IV
and V; it has been decided to include here organoderivatives of silicon and
arsenic, since these are now generally accepted as members of the organo
metallic family, featuring largely, for example, in the Journal of Organometallic
Chemistry and in reviews of the area.
The effects of these changes are shown very clearly in the number of
references to Groups IV and V in successive editions of this book: while the
second and third editions cited 215 and 758 respectively, the present volume
includes 2339. Even so, the problem of selection has been a difficult one,
particulatly with regard to the chapter on silicon. A balance of topics based
solely On the volume of current publications might suggest, for example, that
silicon should be given twenty times the space allotted to antimony. I have
taken the view, however, that sufficient space needs to be given to each ele
ment to establish the principles of its organometallic chemistry.
Since the last edition, there is much new structural information, and I have
sought to include results from most diffraction experiments and selected
spectroscopic measurements. An indication of the synthetic applications of
organo-silicon and -tin compounds in organic chemistry is also given. The
books remains, however, firmly based on the preparation and properties of
individual compounds, for I believe that this is the best approach to an
essentially practical subject.
I am grateful to Professor Geoff Coates and Dr Ken Wade for their most
useful comments, and also to Mrs Bernice Benjamin, Mrs Beryl Drinkwater,
and Miss Julie Wilson for their excellent typing and help with the index.
B. J. AYLETT
CONTENTS
Preface page v
GROUP IV
Silicon, Germanium, Tin, and Lead
1 Introduction 1
2 Silicon 5
Tetra-alkyls and tetra-aryls of silicon 7
Unsaturated organosilicon compounds 14
Heterocyclic compounds of silicon and carbon 21
Cyclic saturated organosilanes 21
Cyclic unsaturated organosilanes 28
Organosilicon(n) compounds and organosilicon radicals 31
Organosilicon halogen compounds 35
Monohalides, R SiX 36
3
Dihalides, R SiX 47
2 2
Trihalides, RSiX 50
3
Organosilicon pseudohalides 55
Organosilicon oxygen compounds 59
Silanols 60
Silanolates or siIoxy-metal derivatives 63
Alkoxides and aryloxides 67
Siloxanes 69
Silicones 75
Short-lived R Si=O intermediates 77
2
Peroxides 77
Ketones 78
Organosilicon sulphur, selenium, and tellurium compounds 81
Organosilicon nitrogen compounds 84
Aminosilanes 85
Disilazanes 88
Cyclic silicon-nitrogen compounds 93
Hydrazine derivatives 96
Organosilylazenes 97
Derivatives of hydroxylamine and ami des 99
Silatranes 100
Organosilicon phosphorus, arsenic, antimony, and bismuth compounds 102
vii
Vlll CONTENTS
Organosilicon hydrides 105
Compounds containing silicon-silicon bonds III
Acyclic derivatives III
Cyclic derivatives 114
Organosilicon-metal compounds 117
Groups I and II 117
Groups III and IV 121
Transition-metal derivatives 123
Silylmethyl-transition-rtletal derivatives 128
3 Germanium 131
Tetra-alkyls and tetra-aryls of germanium 132
Unsaturated organogermanium compounds 135
Heterocyclic compounds of germanium and carbon 137
Organogermanium(n) compounds and organogermanium radicals 139
Organogermanium halogen compounds 140
Monohalides, R GeX 140
3
Dihalides, R GeX 142
2 2
Trihalides, RGeX 144
3
Alkylgermanes with halogenated side-chains 144
Organogermanium pseudohalides 145
Organogermanium oxygen compounds 146
Oxides and hydroxides 146
Alkoxides 149
Peroxides 151
Esters 151
Ketones 151
Organogermanium sulphur, selenium, and tellurium compounds 152
Organogermanium nitrogen compounds 154
Organogermanium phosphorus, arsenic, antimony, and bismuth 157
compounds
Organogermanium hydrides 158
Compounds containing germanium-germanium bonds 163
Organogermanium-metal compounds 166
Alkali-metal and magnesium derivatives 166
Derivatives of other main-group metals 169
Transition-metal derivatives 171
4 Tin 177
Tetra-alkyls and tetra-aryls of tin 179
Unsaturated organotin compounds 187
Heterocyclic compounds of tin and carbon 192
Organotin(n) compounds and organotin radicals 194
Organotin halogen compounds 198
Monohalides, R SnX 201
3
Dihalides, R SnX 205
2 2
Trihalides, RSnX 208
3
CONTENTS m
Complexes of organotin halides 209
Organotin(n) halides 214
Organotin pseudohalides 215
Organotin oxygen compounds 218
Monohydroxides and derivatives 218
Alkoxy and aryloxy derivatives, R SnOR 222
3 1
Dihydroxides and derivatives 225
Tetra-alkyl distannoxanes, (XR SnhO, and related derivatives 227
2
Stannonic acids 229
Peroxides 230
Sn-O compounds in organic synthesis 231
Organotin sulphur, selenium, and tellurium compounds 233
Organotin nitrogen compounds 236
Organotin phosphorus, arsenic, antimony, and bismuth compounds 241
Organotin hydrides 243
Hydrostannation 247
Hydrostannolysis 251
Use of organotin hydrides in synthesis 252
Compounds containing tin-tin bonds 254
Derivatives of distannane 254
Derivatives of hexa-alkyl or -aryl-ditin compounds 257
Derivatives of higher stannanes 259
Derivatives of the type (R Sn)n 260
2
Organotin-metal compounds 264
Alkali-metal derivatives 264
Derivatives of other main-group elements 269
Transition-metal derivatives 271
5 Lead 277
Tetra-alkyls and tetra-aryls of lead 278
Unsaturated organolead compounds 288
Organolead(n) compounds and organolead radicals 290
Organolead halogen compounds 291
Monohalides, R PbX 292
3
Dihalides, R PbX 294
2 2
Trihalides, RPbX 295
3
Organolead oxygen compounds 296
Organolead sulphur, selenium, and tellurium compounds 300
Organolead Group V compounds 301
Organolead hydrides 302
Compounds containing lead-lead bonds 304
Dilead derivatives 304
(R Pb)x derivatives 308
2
Organolead-metal compounds 309
Alkali-metal derivatives 309
Transition-metal derivatives 310
References: Group IV 313
x CONTENTS
GROUP V
Arsenic, Antimony, and Bismuth
6 Introduction 387
7 Arsenic 390
Tri-alkyls and tri-aryls of arsenic 390
Unsaturated organo!arsenic compounds 396
Penta-alkyls and penta-aryls of arsenic 401
Ylides of arsenic 402
Organoarsenic halogen compounds 404
Derivatives of arsenic(v) 404
Arsonium salts 404
Dihalides, R3AsX2 406
Trihalides, R2AsX3 408
Tetrahalides, RAsX4 409
Complexes of Arsenic(v) halides 409
Derivatives or arsenic(m) 410
Monohalides, R2AsX 410
Dihalides, RAsX2 411
Organoarsenic oxygen, sulphur, and selenium compounds 413
Oxygen derivatives of arsenic(v) 413
Tetraorgano hydroxides, R4AsOH 413
Triorgano oxides, R3AsO 414
Triorgano hydroxy-halides, R3As(OH)X 416
Arsinic acids, R2AsO(OH) 418
Arsonic acids, RAsO(OHh 420
Sulphur and selenium derivatives of arsenic(v) 423
Derivatives of arsenic(m) 424
Arsonous acids, RAs(OHh and related derivatives 426
Organoarsenic nitrogen compounds 429
Derivatives of arsenic(v) 429
Derivatives of arsenic(m) 430
Organoarsenic hydrides 431
Compounds containing arsenic-arsenic bonds 434
Diarsines, R2AsAsR2 434
Polyorganoarsines and related compounds 437
Organoarsenic-metal compounds 443
Alkali-metal derivatives 443
Transition-metal derivatives 445
8 Antimony 447
Tri-alkyls and tri-aryls of antimony 447
Unsaturated organoantimony compounds 452
Penta-alkyls and penta-aryls of antimony 455
Ylides of antimony 458
Organoantimony halogen compounds 458
Derivatives of antimony(v) 458
CONTENTS ri
Stibonium salts, R SbX 458
4
Dihalides, R SbX 460
3 2
Trihalides, R SbX 462
2 3
Tetrahalides, RSbX 463
4
Complexes of antimony(v) halides 463
Derivatives of antimony(m} 465
Monohalides, R SbX 465
2
Dihalides, RSbX 466
2
Organoantimony oxygen, sulphur and selenium compounds 467
Oxygen derivatives of antimony(v} 467
Tetraorgano hydroxides, R SbOH, and alkoxy compounds, Rs_xSb(OR)x 467
4
Triorgano oxides, R SbO 468
3
Stibinic acids, R SbO(OH) 470
2
Stibonic acids, RSbO(OHh 470
Sulphur and selenium derivatives of antimony(v} 471
Derivatives of antimony(m} 472
Organoantimony hydrides 473
Compounds containing antimony-antimony bonds 474
Organoantimony-metal compounds 476
9 Bismuth 479
Tri-alkyls and tri-aryls of bismuth 479
Unsaturated organobismuth compounds 483
Penta-aryls of bismuth 484
Organobismuth halogen derivatives 486
Derivatives of bismuth(v} 486
Derivatives of bismuth(m} 487
Organobismuth-metal compounds 489
References: Group V 490
Subject index 508
