Applications of Organometallic Compounds

Iwao Omae

Omae Research Laboratories, Japan

Copyright 1998 by

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British Library Cataloguing in Publication Data

A catalogue record for this book is available from the British Library

ISBN 0 471 97604 0

Typeset in 10/12pt Times by Techset Composition Limited, SalisburyPrinted and bound in Great Britain by Biddles Ltd, Guildford and King's Lynn

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Contents

Preface vii

1Introduction

1

2History of Organometallic Chemistry

9

3Organolithium Compounds

27

4Organomagnesium Compounds

49

5Organozinc Compounds

73

6Organoboron Compounds

91

7Organoaluminum Compounds

107

8Organosilicon Compounds

127

9Organogermanium Compounds

165

10Organotin Compounds

185

11Organolead Compounds

215

12Organotitanium Compounds

229

13Organochromium Compounds

253

14Organomanganese Compounds

281

15Organoiron Compounds

303

16Organoruthenium Compounds

335

17Organocobalt Compounds

363

18Organorhodium Compounds

385

19Organonickel Compounds

411

20Organopalladium Compounds

435

21Organoplatinum Compounds

467

22Organocopper Compounds

489

Index 509

Preface

Organometallic compounds are used not only by organometallic chemists but also organic syntheticchemists, natural products synthetic chemists, pharmaceutical synthetic chemists and perfumesynthetic chemists in synthetic reactions as catalysts or as reagents. As the properties of theorganometallic compounds have gradually become apparent, many new synthetic methods usingorganometallic compounds have been discovered. In many cases, the desired compounds have beensynthesized via many reaction steps, and the reactions involved two or more kinds of organometalliccompounds or inorganic metallic compounds such as PdCl2 and RhCl(PPh3)3. Since the latterinorganic metallic compounds in most cases act as catalysts for the organometallic compounds havinga metal-carbon bond in the course of the reaction, the reactions using these inorganic metalliccompounds are thus also considered to the organometallic reactions.

Since there are many kinds of organometallic compounds and these have different properties, then weshould first of all understand the properties of each organometallic compound before using thesecompounds in synthetic reactions. However, at present, even if a person decides to investigate theseproperties, there are few books dealing with these compounds.

This book was compiled by mainly putting together reviews on nine representative main grouporganometallic compounds and eleven transition metal organometallic compounds, and it includestheir histories of utilization. These reviews have been published in Kagaku Kogyo (Chemical Industry)in the September 1990 to March 1996 issues. This book also includes more recent articles. Tounderstand these organometallic compounds a comprehensive knowledge of metallic elements isrequired. Therefore this book is designed to show the properties of each metallic element. Sidereactions caused by impurities in each organometallic reagent are often regarded as significant insynthetic reactions and probably many investigators have gone through many difficulties. This bookshows the production process of each metal in order to give knowledge to the reader on the possibleimpurities on each metal.

This book is intended as an introduction for research chemists who want to understand the outline ofeach of the organometallic compounds, and hopefully is of value to undergraduate students, graduatestudents and research workers as well.

Finally, I should like to express my sincere gratitude to Dr. Sumio Chubachi for reading the fullmanuscript, which enhanced its accuracy and clarity, and for providing much valuable constructivecriticism.

CoverTitleContentsPreface1 Introduction2 History of Organometallic Chemistry3 Organolithium Compounds4 Organomagnesium Compounds5 Organozinc Compounds6 Organoboron Compounds7 Organoaluminum Compounds8 Organosilicon Compounds9 Organogermanium Compounds10 Organotin Compounds11 Organolead Compounds12 Organotitanium Compounds13 Organochromium Compounds14 Organomanganese Compounds15 Organoiron Compounds16 Organoruthenium Compounds17 Organocobalt Compounds18 Organorhodium Compounds19 Organonickel Compounds20 Organopalladium Compounds21 Organoplatinum Compounds22 Organocopper Compounds