Advances in ORGANOMETALLIC CHEMISTRY VOLUME I I ADVISORY BOARD H. J. EMELEUS HENRY GILMAN CONTRIBUTORS TO THIS VOLUME Herbert C. Brown M. I. Bruce P. J. Craig C. S. Cundy B. M. Kingston M. F. Lappert Alexander McKiIlop J. M. Pratt Edward C. Taylor Paul M. Treichel D. R. Wiles Andrew Wojcicki Advances in ORGANOME TALLIC CHEMISTRY EDITED BY ROBERT WEST F. G. A. STONE DEPARTMENT OF INORGANIC CHEMISTRY THE UNIVERSITY BRISTOL, ENGLAND DEPARTMENT OF CHEMISTRY UNIVERSITY OF WISCONSIN MADISON, WISCONSIN VOLUME I I I973 ACADEMIC PRESS New York London 1973, BY ACADEMIC PRESS, INC. COPYRIGHT ALL RIGHTS RESERVED. NO PART OF THIS PUBLICATION MAY BE REPRODUCED OR TRANSMI'lTED IN ANY FORM OR BY ANY MEANS, ELECTRONIC OR MECHANICAL, INCLUDING PHOTOCOPY, RECORDING, OR ANY INFORMATION STORAGE AND RETRIEVAL SYSTEM, WITHOUT PERMISSION IN WRITING FROM THE PUBLISHER. ACADEMIC PRESS, INC. 111 Fifth Avenue, New York,New York 10003 United Kingdom Edition published by ACADEMIC PRESS, INC. (LONDON)LTD. 24/28 Oval Road, London NWl LIBRARY OF CONGRESS CATALOG CARD NUMBER:64 - 16030 PRINTED IN THE UNITED STATES OF AMERICA Contents LIST OF CONTRIBUTORS ERRATUM. . . ix xi . . 1 3 Boranes in Organic Chemistry HERBERT C. BROWN Introduction . Diborane as a Reducing Agent . Volatile Compounds of Uranium . . The Alkali Metal Hydride Approach to Diborane . Alkali Metal Borohydrides . Molecular Addition Compounds and Steric Strains VII. Steric Assistance in Solvolysis . VIII. The Nonclassical Ion Problem . . IX. Selective Reductions . X. Hydroboration . . XI. T h e Versatile Organoboranes . XII. Conclusion References . I. 11. 111. IV. V. VI. . . 4 . . . . 5 6 7 8 . 9 . . 11 12 . . . 14 17 18 . . . 21 23 28 . . 81 Transition Metal-lsocyanide Complexes PAUL M. TREICHEL Introduction . Structure and Bonding . Current Topics. . Isocyanide Complexes of Various Metals References . I. 11. 111. IV. . 49 Insertion Reactions of Transition Metal-Carbon u-Bonded Compounds I :Carbon Monoxide Insertion ANDREW W O JCICKI I. 11. 111. IV. V. VI. . Introduction to and Scope of Insertion Reactions . Carbon Monoxide Insertion. General Considerations and Background Kinetics and Mechanism of Carbon Monoxide Insertion . . Kinetics and Mechanism of Decarbonylation . . Stereochemistry of Carbonylation and Decarbonylation . Survey of Reactions . References . V . 88 . 90 . 94 . 105 . 112 . 117 . 139 Contents vl Recent Advances in Organothallium Chemistry ALEXANDER McKlLLOP and EDWARD C. TAYLOR I. Introduction . 11. Organothallium(1) Compounds 111. Organothallium(II1) Compounds References . . . . . . . . . \ . 147 148 155 202 The Radiochemistry of Organometallic Compounds D. R. WILES I. Introduction . 11. Chemical Effects of Nuclear Transformations 111. Survey of Experimental Results . IV. Discussion . References . . . . . 207 208 221 237 249 Organometallic Complexes with Silicon-Transition Metal or Silicon-Carbon-Transition Metal Bonds C. S. CUNDY, B. M. KINGSTON, and M. F. LAPPERT I. Introduction . . 11. Organometallic Complexes with Silicon-Transition Metal Bonds . . 111. Transition Metal-Catalyzed Homogeneous Hydrosilylation . , IV. Organometallic Complexes with Silicon-Carbon-Transition Metal Bonds . References . . References Added in Proof . . 253 254 297 310 323 330 . . Preparati