ORGANOMETALLIC COMPOUNDS

Transcription

1 ORGANOMETALLIC COMPOUNDS VOLUME ONE THE MAIN GROUP ELEMENTS PART TWO Groups IV and V

2 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

3 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

4 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 B. J. Aylett Softcover reprint of the hardcover 1 st edition 1979 ISBN-13: e-isbn-13: DOI: / 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 of John 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 QD New York, USA Halsted Press

5 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 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 organometallic 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 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 element 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

6 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 3SiX Dihalides, R 2SiX Trihalides, RSiX 3 50 Organosilicon pseudohalides 55 Organosilicon oxygen compounds 59 Silanols 60 Silanolates or siioxy-metal derivatives 63 Alkoxides and aryloxides 67 Siloxanes Silicones Short-lived R 2Si=O intermediates 77 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

7 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 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 3 GeX 140 Dihalides, R2GeX Trihalides, RGeX 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 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 3SnX 201 Dihalides, R2SnX Trihalides, RSnX3 208

8 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 3SnOR Dihydroxides and derivatives 225 Tetra-alkyl distannoxanes, (XR2SnhO, and related derivatives 227 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 2Sn)n 260 Organotin-metal compounds 264 Alkali-metal derivatives 264 Derivatives of other main-group elements 269 Transition-metal derivatives 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 3PbX 292 Dihalides, R 2PbX2 294 Trihalides, RPbX 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 (R2Pb)x derivatives 308 Organolead-metal compounds 309 Alkali-metal derivatives 309 Transition-metal derivatives 310 References: Group IV 313

9 x CONTENTS 6 Introduction GROUP V Arsenic, Antimony, and Bismuth 7 Arsenic Tri-alkyls and tri-aryls of arsenic Unsaturated organo!arsenic compounds Penta-alkyls and penta-aryls of arsenic Ylides of arsenic Organoarsenic halogen compounds Derivatives of arsenic(v) Arsonium salts Dihalides, R3AsX2 Trihalides, R2AsX3 Tetrahalides, RAsX4 Complexes of Arsenic(v) halides Derivatives or arsenic(m) Monohalides, R2AsX Dihalides, RAsX2 Organoarsenic oxygen, sulphur, and selenium compounds Oxygen derivatives of arsenic(v) Tetraorgano hydroxides, R4AsOH Triorgano oxides, R3AsO Triorgano hydroxy-halides, R3As(OH)X Arsinic acids, R2AsO(OH) Arsonic acids, RAsO(OHh Sulphur and selenium derivatives of arsenic(v) Derivatives of arsenic(m) Arsonous acids, RAs(OHh and related derivatives Organoarsenic nitrogen compounds Derivatives of arsenic(v) Derivatives of arsenic(m) Organoarsenic hydrides Compounds containing arsenic-arsenic bonds Diarsines, R2AsAsR2 Polyorganoarsines and related compounds Organoarsenic-metal compounds Alkali-metal derivatives Transition-metal derivatives 8 Antimony Tri-alkyls and tri-aryls of antimony Unsaturated organoantimony compounds Penta-alkyls and penta-aryls of antimony Ylides of antimony Organoantimony halogen compounds Derivatives of antimony(v)

10 CONTENTS ri Stibonium salts, R 4 SbX 458 Dihalides, R 3SbX Trihalides, R 2SbX Tetrahalides, RSbX Complexes of antimony(v) halides 463 Derivatives of antimony(m} 465 Monohalides, R 2SbX 465 Dihalides, RSbX Organoantimony oxygen, sulphur and selenium compounds 467 Oxygen derivatives of antimony(v} 467 Tetraorgano hydroxides, R 4 SbOH, and alkoxy compounds, Rs_xSb(OR)x 467 Triorgano oxides, R 3SbO 468 Stibinic acids, R 2 SbO(OH) 470 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 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