Applications of Organometallic Compounds

Applications of Organometallic Compounds Iwao Omae Omae Research Laboratories, Japan

Copyright © 1998 by John Wiley & Sons Ltd, Baffins Lane, Chichester, West Sussex PO19 1UD, England National 01243 779777 International (+44) 1243 779777 e-mail (for orders and customer service enquiries): cs-books@w iley.co.uk Visit our Home Page on http://www.wiley.co.uk or http://www.wiley.com Reprinted March 1999 All Rights Reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, scanning or otherwise, except under the terms of the Copyright, Designs and Patents Act 1988 or under the terms of a licence issued by the Copyright Licensing Agency, 90 Tottenham Court Road, London, UK W1P 9HE, without the permission in writing of the Publisher. Other Wiley Editorial Offices John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158-0012, USA WILEY-VCH Verlag GmbH, Pappelallee 3, D-69469 Weinheim, Germany Jacaranda Wiley Ltd, 33 Park Road, Milton, Queensland 4064, Australia John Wiley & Sons (Asia) Pte Ltd, 2 Clementi Loop #02-01, Jin Xing Distripark, Singapore 129809 John Wiley & Sons (Canada) Ltd, 22 Worcester Road, Rexdale, Ontario M9W 1L1, Canada 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, Salisbury Printed and bound in Great Britain by Biddles Ltd, Guildford and King's Lynn This book is printed on acid-free paper responsibly manufactured from sustainable forestry, in which at least two trees are planted for each one used for paper production.

Contents Preface

vii

1 Introduction

1

2 History of Organometallic Chemistry

9

3 Organolithium Compounds

27

4 Organomagnesium Compounds

49

5 Organozinc Compounds

73

6 Organoboron Compounds

91

7 Organoaluminum Compounds

107

8 Organosilicon Compounds

127

9 Organogermanium Compounds

165

10 Organotin Compounds

185

11 Organolead Compounds

215

12 Organotitanium Compounds

229

13 Organochromium Compounds

253

14 Organomanganese Compounds

281

15 Organoiron Compounds

303

16 Organoruthenium Compounds

335

17 Organocobalt Compounds

363

18 Organorhodium Compounds

385

19 Organonickel Compounds

411

20 Organopalladium Compounds

435

21 Organoplatinum Compounds

467

22 Organocopper Compounds

489

Index

509

Preface Organometallic compounds are used not only by organometallic chemists but also organic synthetic chemists, natural products synthetic chemists, pharmaceutical synthetic chemists and perfume synthetic chemists in synthetic reactions as catalysts or as reagents. As the properties of the organometallic compounds have gradually become apparent, many new synthetic methods using organometallic compounds have been discovered. In many cases, the desired compounds have been synthesized via many reaction steps, and the reactions involved two or more kinds of organometallic compounds or inorganic metallic compounds such as PdCl2 and RhCl(PPh3)3. Since the latter inorganic metallic compounds in most cases act as catalysts for the organometallic compounds having a metal-carbon bond in the course of the reaction, the reactions using these inorganic metallic compounds are thus also considered to the organometallic reactions. Since there are many kinds of organometallic compounds and these have different properties, then we should first of all understand the properties of each organometallic compound before using these compounds in synthetic reactions. However, at present, even if a person decides to investigate these properties, there are few books dealing with these compounds. This book was compiled by mainly putting together reviews on nine representative main group organometallic compounds and eleven transition metal organometallic compounds, and it includes their 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. To understand these organometallic compounds a comprehensive knowledge of metallic elements is required. Therefore this book is designed to show the properties of each metallic element. Side reactions caused by impurities in each organometallic reagent are often regarded as significant in synthetic reactions and probably many investigators have gone through many difficulties. This book shows the production process of each metal in order to give knowledge to the reader on the possible impurities on each metal. This book is intended as an introduction for research chemists who want to understand the outline of each of the organometallic compounds, and hopefully is of value to undergraduate students, graduate students and research workers as well. Finally, I should like to express my sincere gratitude to Dr. Sumio Chubachi for reading the full manuscript, which enhanced its accuracy and clarity, and for providing much valuable constructive criticism.