Advances in ORGANOMETALLIC CHEMISTRY VOLUME 35 This Page Intentionally Left Blank Advances in Organometallic Chemistry EDITED BY F. G. A. STONE ROBERT WEST DEPARTMENTOF CHEMISTRY DEPARTMENTOF CHEMISTRY UNIVERSITYOF WISCONSIN BAYLOR UNIVERSITY MMISON. WISCONSIN WACO. TEXAS VOLUME 35 ACADEMIC PRESS, INC. A Division of Harcoun Brace & Company San Diego New York Boston London Sydney Tokyo Toronto This book is printed on acid-free paper, @ Copyright 0 1993 by ACADEMIC PRESS, INC. All Rights Reserved. No part of this publication may be reproduced or transmitted 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. 1250 Sixth Avenue, San Diego, California 92101-431 1 United Kingdom Edition published by Academic Press Limited 24-28 Oval Road, London NWl 7DX International Standard Serial Number: 0065-3055 International Standard Book Number: 0-12-03 1135-6 PRINTED IN THE UNITED STATES OF AMERICA 9 3 9 4 9 5 9 6 9 7 9 8 BB 9 8 7 6 5 4 3 2 1 CONTRIBUTORS . . . . . . . . . . . . . . . . . . . . . . . . . vii Chemistry at Diplatinum Centers GORDON K . ANDERSON I. I1. I11. IV. V. VI. VII. VIII . Introduction . . . . . . . . . . . . . . . . . . . . . . . ComplexeswithUnsupportedPlatinum-PlatinumBonds . . . . . . . Halide- and Hydride-Bridged Complexes . . . . . . . . . . . . . Complexes Containing Organic Bridging Groups . . . . . . . . . . Complexes Containing Orthometalated Phosphine Ligands . . . . . . . Complexes Bridged by dppm or Related Ligands . . . . . . . . . . Complexes Bridged dppc Ligands. . . . . . . . . . . . . . . . Summary . . . . . . . . . . . . . . . . . . . . . . . . References. . . . . . . . . . . . . . . . . . . . . . . . 1 1 2 5 7 11 32 35 35 Transition Metal Clusters in Homogenous Catalysis G. SUSS-FINK and G. MEISTER . . . . . . . . . . . . . . . 111. Catalytic Reactions Involving H, . . . . IV. Catalytic Reactions Involving CO and H, . . . . . V. Catalytic Reactions Involving CO and H,0 . VI. Other Catalytic Reactions . . . . . . . VII. Conclusions . . . . . . . . . . . . . References. . . . . . . . . . . . . . I. Introduction I1. Catalytic Reactions Involving CO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41 44 49 74 95 107 122 122 The Interplay of Alkylidyne and Carbaborane Ligands at Metal Centers II: Proton-Mediated Reactions STEPHEN A. BREW and F.GORDON A. STONE I . Introduction . . . . . . . . . . . . . . . . . . . . . . . . I11. Protonations with HBF4.Etz0 in the Presence of Bidentate Phosphines . . IV . Protonations with HX (X = C1 or I) . . . . . . . . . . . . . . . . V. Formation of Dimetal Compounds . . . . . . . . . . . . . . . VI. Exa-nido Metallacarbaboranes. . . . . . . . . . . . . . . . . VII. Spectroscopic and X-RayDiffraction Analysis . . . . . . . . . . . VIII. Conclusions . . . . . . . . . . . . . . . . . . . . . . . References. . . . . . . . . . . . . . . . . . . . . . . . I1. Protonations with HBF4.Et,0 in the Presence of Monodentate Lewis Bases V 135 142 149 152 157 172 176 183 183 vi Contents Di- and Trinuclear Metal Complexes of Diboraheterocycles WALTER SIEBERT I. I1. I11. IV. V. VI. VII . Introduction . . . . . . . . . . . . . . . . . 1. 4Di