Organometallic Compounds: Volume One The Main Group Elements Part Two Groups IV and V PDF
Preview Organometallic Compounds: Volume One The Main Group Elements Part Two Groups IV and V
ORGANOMETALLIC 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
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