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Transition Metal Carbyne Complexes NATO ASI Series Advanced Science Institutes Series Transition Metal Carbyne Complexes NATO ASI Series Advanced Science Institutes Series A Series presenting the results of ectivities sponsored by the NATO Science Committee, which aims at the dissemination ofadvanced scientitic and technological knowledge, with a view to strengthening links between scientific communities. The Series is published by an international board of publishers in conjunction with the NATO Scientific Affairs Division A Life Sciences Plenum Publishing Corporation B Physics London and New York C Mathematical Kluwer Academic Publishers and Physical Sciences Dordrecht, Boston and London O Behavioural and Social Sciences E Applied Sciences F Computer and Systems Sciences Springer-Verlag G Ecological Sciences Berlin, Heidelberg, New York, London, H Cell Biology Paris and Tokyo I Global Environmental Change NATO-PCO-DATA BASE The electronic index to the NATO ASI Series provides full bibliographical references (with keywords andlor abstracts) to more than 30000 contributions from international scientists published in aII sections of the NATO ASI Series. Access to the NATO-PCO-DATA BASE is possible in two ways: - via online FILE 128 (NATO-PCO-DATA BASE) hosted by ESRIN, Via Galileo Galilei, 1-00044Frascati, Italy. - via CD-ROM "NATO-PCO-DATA BASE" with user-friendly retrieval software in English, French and German (© WTV GmbH and DATAWARE Technologies Inc. 1989). The CD-ROM can be ordered through any member of the Board of Publishers or through NATO-PCO, Overijse, Belgium. Series C: Mathematical and Physical Sciences - VoI. 392 Transition Metal Carbyne Complexes edited by F. R. KreiBI Anorganisch-Chemisches Institut, Technische Universităt Munchen, Garching, Germany Springer Science+Business Media, B.V. Proceedings of the NATD Advanced Research Workshop on Transition Metal Carbyne Complexes Wildbad Kreuth, Germany September 27-Dctober 2,1992 ISBN 978-94-010-4728-9 ISBN 978-94-011-1666-4 (eBook) DOI 10.1007/978-94-011-1666-4 Printed on acid-free paper AII Rights Reserved © 1993 Springer Science+Business Media Dordrecht Originally published by Kluwer Academic Publishers in 1993 Softcover reprint of the hardcover 1st edition 1993 No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, inciuding photo­ copying, recording or by any information storage and retrieval system, without written permission from the copyright owner. Table of Contents Preface IX Foreword XI List of Participants XV OLEFIN METATHESIS BY WELL-CHARACTERIZED RE(VII) ALKYLIDENE/ALKYLIDYNE COMPLEXES R. R. Schrock, R. Toreki, G. A. Vaughan, A. Farooq PROTONATION REACTIONS OF ALKYLIDYNE(CARBABORANE) COMPLEXES OF THE GROUP 6 METALS S. A. Brew, N. Carr, F. G. A. Stone 23 CYCLOMETALATED ARYLOXY(CHLORO)NEOPENTYLIDENE-TUNGSTEN COMPLEXES. SYNTHESES FROM NEOPENTYLIDYNE COMPLEXES AND CATALYTIC PROPERTIES IN OLEFIN METATHESIS J.-L. Couturier, M. Leconte, J.-M. Basset 39 REACTION OF SOME ALKYLIDYNE COMPLEXES OF TUNGSTEN WITH INORGANIC OXIDES: A GENERAL ROUTE TOWARDS ACTIVE SUPPORTED W BASED METATHESIS CATALYSTS? R. Buffon, M. Leconte, A. Choplin, J.-M. Basset 51 ON THE ROUTE FROM STOICHIOMETRIC TO CAT AL YTIC REACTIONS OF CARBYNE COMPLEXES. Part XX (1) K. Weiss, R. Goller, M. Denzer, G. LoBel, J. KOdel 55 YLIDE NICKEL CATALYSIS: PROGRESS IN ACETYLENE POLYMERIZATION K. A. Ostoja Starzewski 67 CONmGATED COMPLEXES AND POLYMERS DERIVED FROM METAL­ ALKYLIDYNE BUILDING BLOCKS T. P. Pollagi, J. Manna, T. C. Stoner, S. J. Geib, M. D. Hopkins 71 vi METHYLIDYNE COMPLEXES: STRUCTURES, SPECTRA, AND BONDING J. Manna, L. A. Mlinar, R. J. Kuk, R. F. Dallinger, S. J. Geib, M. D. Hopkins 75 NOVEL CYCLIZATIONS INVOLVING CATIONIC CARBYNE COMPLEXES H. Fischer, C. Troll, J. Schleu 79 NEW ADDITION AND CYCLOADDITION REACTIONS OF THE CAnONIC CARBYNE COMPLEXES [Cp(CO)(L)M=CR]+ (M = Mn, Re; L = CO, PPh3; R = Me, Tolyl) G. L. Geoffroy, C. Kelley, L. A. Mercando, M. R. Terry, N. Lugan, C. Yi, A. Kaplan 85 ALKYNYLCARBENE COMPLEXES OF TRANSITION METALS AS SUITABLE SUBSTRATES FOR STEREOSELECnVE CYCLOADDITIONS L. Jordi, A. Llebaria, S. Ricart, J. M. Vinas, J. M. Moret6 97 REACTION OF ALKYNOLS WITH ALKYNYLALKOXYCARBENE METAL (Cr,W) COMPLEXES J. M. Vinas, J. M. Moret6, S. Ricart 101 CHEMISTRY AND ELECTROCHEMISTRY OF ALKYNE- AND ISO­ CYANIDE-DERlVED CARBYNE COMPLEXES OF RHENIUM, MOLYBDENUM OR TUNGSTEN A. J. L. Pombeiro 105 PHOTOOXIDATION OF MOLYBDENUM AND TUNGSTEN CARBYNES L. McElwee-White, K. B. Kingsbury, J. D. Carter 123 THE DETERMINAnON OF THE CHEMICAL BONDS IN SOME METAL­ CARBYNE COMPLEXES BY STRUCTURAL STUDIES Nguyen Quy Dao 127 PLANAR TETRACOORDIONATE CARBON- EXPERlMENTAL DETERMINA nON OF THE CHARGE DENSITY OF Cp2Zr(Il-1l1,1l2-Me3SiCCPh)(Il-CI)AIMe2 (I) AND CP2Zr(Il-1l1,1l2-MeCCPh)(Il-CCPh)AIMe2 (II) C. KrUger, S. Werner 131 vii CARBYNE TO CARBENE LIGAND CONVERSION IN DINUCLEAR COMPLEXES L. Busetto, V. Zanotti, S. Bordoni, L. Carlucci, A. Palazzi 137 SYNTIlESES AND REACTIONS OF HETERODINUCLEAR ALKOXYCARBYNE COMPLEXES W. H. Hersh 149 MULTICENTER LIGAND TRANSFORMATIONS OF TETRAMETHYL­ THIOUREA ON RUTHENIUM CLUSTERS G. Suss-Fink 151 CARBYNE COMPLEXES OF RUTHENIUM AND OSMIUM W. R. Roper 155 TOWARDS THE SYNTHESIS OF CARBYNE COMPLEXES OF GOLD AND COPPER: NEW CARBENE COMPLEXES H. G. Raubenheimer, S. Cronje, R. Otte, W. Van Zyl, I. Taljaard, P. Olivier 169 DOUBLE AND TRIPLE BONDS TO f-ELEMENTS: STRUCTURE AND CHEMISTRY OF ACTINIDE COMPLEXES OF MULTIELECTRON PAIR DONOR LIGANDS J. W. Gilje, R. E. Cramer 175 METAL CARBENES AND METAL CARBYNES AS PRECURSORS FOR A RATIONAL SYNTHESIS OF CARBIDO AND HYDROCARBON BRIDGED COMPLEXES W. Beck, J. Breimair, P. Fritz, W. Knauer, T. Weidmann 189 SOME CHEMISTRY OF Tp'(COhW=C-H, A SIMPLE TERMINAL CARBYNE G. M. Jamison, P. S. White, D. L. Harris, J. L. Templeton 201 THE ROLE OF NUCLEOPHILES AND ELECTROPHlLES IN COUPLING REACTIONS OF ALKYLIDYNE LIGANDS A. Mayr 219 viii DICARBONYL(1l5-CYCLOPENTADIENYL)CARBYNE COMPLEXES OF MOLYBDENUM AND TUNGSTEN AS Burr.DING BLOCKS F. R. KreiBl, J. Ostermeier, W. Schlitt, C. M. Stegmair, N. Ullrich, W. Ullrich 231 DIVERSIONS EN ROUTE TO ALKYLIDYNE COMPLEXES OF IRON A. F. Hill 239 ELECTRON-RICH TUNGSTEN AMINOCARBYNE COMPLEXES WITH Cp*LIGANDS SYNTHESIS AND PROTONATION REACTIONS B. Lungwitz, A. C. Filippou 249 Index 255 Preface The chemistry of transition metal carbyne complexes has become a highly attractive field during the past twenty years. In recent years its application to aspects of catalysis and metathesis has gained considerable interest from inorganic as well as organic chemists. In addition, organic synthesis by means of metal carbon multiple bond reagents offers the most sophisticated technology currently available. In consideration of these developments some of Professor E. O. Fischer's former coworkers and colleagues felt obliged to orga­ nize this NATO Advanced Research Workshop on Transition Metal Carbyne Complexes in the Bavarian Alps. They have been encouraged by the fact that most of the distinguished scientists in the field of metal-carbon multiple bond chemistry had finally agreed to participate and to present stimulating lectures. The organizers of the workshop are deeply grateful to the Scientific Affairs Division of the NATO for the generous financial support of the meeting in Wildbad Kreuth and for the preparation of this book. They also feel indebted to acknowledge the generous support from Wacker-Chemie, BASF, Peroxid-Chemie, Hoechst and Bayer. Finally they thank the staff of the Hanns-Seidel-Stiftung in Wildbad Kreuth for providing a pleasant and stimu­ lating atmosphere during the meeting. Fritz R. KreiBl Technische Universitat Miinchen ix Foreword It is not easy these days to put a focus on the rapid development of the chemistry related to metal-carbene and metal-carbyne complexes. This area of scientific research and tech­ nology has become so broad in scope and so high in knowledge that it is necessary to apply this focus by means of scientific meetings. The NATO Series of scientific conferences - another pieceful way of spending public money out of the defense budget - have greatly added to the development of high-techno­ logy research areas during the past decades. Organometallic chemistry has developed on this time-scale and has received great benefit from programmes like the NATO Series. Modelled after the success of a previous meeting on "Metal-Carbene Complexes", Professor KreiBl organized the consecutive conference on "Metal-Carbyne Complexes" nearby the cradle of these versatile, successful, chemically as well as industrially useful species: At Technische Universitlit Milnchen, Professor Ernst Otto Fischer was holding the chair of Inorganic Chemistry over a period of twenty years - from 1964 (following Walter Hieber) until 1984. Ernst Otto Fischer is one of the pioneers of organometallic chemistry. In Europe, he and Franz Hein, Karl Ziegler, Walter Hieber, Geoffrey Wilkinson, and Georg Wittig made the most eminent personal contributions to this highly interdisciplinary field of research. These days, catalysis, organic synthesis and materials science are the major areas of appli­ cation, with the latter segment being in rapid expansion. The basis of all these appli­ cations, however, remains to be synthesis and structure. Professor Fischer has mastered both areas ever since he entered the exciting field of organometallic chemistry through ferrocene (structure) and dibenzene chromium (synthesis). In later years he succeeded to synthesize the first organometallic compound exhibiting a metal-to-carbon triple bond - predominantly a result of great and long-lasting enthusiasm. Boron trihalides were thought to substitute a halogen atom for the alkoxy group in one of Fischer's metal carbene com­ pounds of general composition (CO)SM=C(OR')R (M = Cr, Mo, W). Quite unexpectedly in those days, the first carbyne complex resulted when my fellow-student Gerhard Kreis, now a chemist at Wacker-Chemie GmbH (Burghausen/Bavaria), performed the very experiments with utmost precision typical of him. The puzzling but xi xii correct elemental analysis of his new product, (CO)4ClW=C(Cc5Hs), performed by Manfred Barth in our institute is shown in Fig. 1.
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