The Chemistry Of Carbon. Organometallic Chemistry

Comprehensive Inorganic Chemistry EDITORIAL BOARD J. C. BAILAR JR., Urbana H. J. EMELfiUS, F.R.S., Cambridge tSIR RONALD NYHOLM, F.R.S., London A. F. TROTMAN-DICKENSON, Cardiff {Executive Editor) The Chemistry of CARBON A. K. Holliday, G. Hughes and S. M. Walker ORGANOMETALLIC CHEMISTRY M. L. H. Green and P. Powell Chapters 13 and 14 of Comprehensive Inorganic Chemistry PERGAMON PRESS OXFORD SYDNEY . . NEW YORK PARIS . . TORONTO BRAUNSCHWEIG Pergamon Press Offices: U.K. U.S.A. CANADA AUSTRALIA FRANCE WEST GERMANY Pergamon Press Ltd., Headington Hill Hall, Oxford, OX3 OBW, England Pergamon Press Inc., Maxwell House, Fairview Park, Elmsford, New York 10523, U.S.A. Pergamon of Canada Ltd., 207 Queen's Quay West, Toronto 1, Canada Pergamon Press (Aust.) Pty. Ltd., 19a Boundary Street, Rushcutters Bay, N.S.W. 2011, Australia Pergamon Press SARL, 24 rue des Ecoles, 75240 Paris, Cedex 05, France Pergamon Press GmbH, D-3300 Braunschweig, Postfach 2923, Burgplatz 1, West Germany Copyright © Pergamon Press 1973 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, electrostatic, magnetic tape, mechanical, photocopying, recording or otherwise, without permission in writing from the publishers First edition 1973 Reprinted, with corrections, from Comprehensive Inorganic Chemistry, 1975 Library of Congress Catalog Card No. 77-189736 Printed in Great Britain by A. Wheaton & Co, Exeter ISBN 0 08 018786 2 (hard cover) ISBN 0 08 018785 4 (Flexicover) PREFACE The excellent reception that has been accorded to Comprehensive Inorganic Chemistry since the simultaneous publication of the five volumes of the complete work has been accompanied by the plea that sections should be made available in a form that would enable specialists to purchase copies for their own use. To meet this demand the publishers have decided to issue selected chapters and groups of chapters as separate editions. These chapters will, apart from the corrections of misprints and the addition of prefatory material and individual indices, appear just as they did in the main work. Extensive revision would delay publication and greatly raise the cost, so limiting the circulation of these definitive reviews. A. F. TROTMAN-DICKENSON Executive Editor vn 13. CARBON A. K. HOLLIDAY, G. H U G H E S and S. M. WALKER The University of Liverpool 1. T H E E L E M E N T 1.1. GENERAL Carbon, as charcoal from the combustion of wood, has been known to man from prehistoric times. Its name derives from the Latin carbo meaning charcoal. The element is unique in the vast number of its compounds—there are probably more than one million known today. This unique behaviour is in part due to the ability of carbon to form strong chemical bonds not only with itself but with many other elements, particularly those commonly occurring in nature. Some typical bond energy terms are given in Table 1. TABLE 1. BOND ENERGY TERMS 3 FOR CARBON AND SILICON WITH OTHER ELEMENTS X D(C-X), kcal c 83 Si H O N S P Cl Z)(Si- X ) , kcal 53 76 108 98 85 73 65 63 81 70 91 8 T. L. Cottrell, The Strengths of Chemical Bonds, 2nd ed. Butterworths (1958). Also shown in Table 1 for comparison are the corresponding values for silicon. It is apparent that although silicon bonds strongly to other elements the Si-Si bond is relatively weak and there is little correspondence, therefore, in silicon chemistry to the vast range of organic compounds. The marked stability of such a wide range of compounds is in part to be attributed to the electro