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On the Way to Carbene and Carbyne Complexes ERNST OTTO FISCHER

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On the Way to Carbene and Carbyne Complexes ERNST OTTO FISCHER Advances in ORGANOMETALLIC CHEMISTRY VOLUME 14 CONTRIBUTORS TO THIS VOLUME V. G. Albano Kenneth P. Callahan P. Chini Ernst Otto Fischer M. Frederick Hawthorne James A. lbers Steven D. lttel M. F. Lappert P. W. Lednor G. Longoni Yoshio Matsumura Akira Nakamura Rokuro Okawara Sei Otsuka V. S. Petrosyan 0. A. Reutov Hubert Schmidbaur Dietmar Seyferth N. S. Yashina Advances in Organometallic Ch emis tr y EDITED BY F. G. A. STONE ROBERT WEST DEPARTMENT OF INORGANIC CHEMISTRY DEPARTMENT OF CHEMISTRY THE UNIVERSITY UNIVERSITY OF WISCONSIN BRISTOL, ENGLAND MADISON, WISCONSIN VOLUME 14 @ 1976 ACADEMIC PRESS New York * San Francisco * London A Subsidiary of Harcourt Brace Jovanovich, Publishers COPYRIGHT0 1976, BY ACADEMICPRESS, 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. 111 Fifth Avenue, New York. New York 10003 United Kingdom Edition published by ACADEMIC PRESS, INC. (LONDON) LTD. 24/28 Oval Road. London NWI LIBRARYOF CONGRESSCATALOG CARD NUMBER: 64-16030 ISBN 0-12-031114-3 PRINTED IN THE UNITED STATES OF AMERICA Contents LIST OF CONTRIBUTORS . ix PREFACE xi On the Way to Carbene and Carbyne Complexes ERNST OTTO FISCHER I. Introduction . .1 11. Transition Metal-Carbene Complexes . .3 111. Other Syntheses of Cnrbene Complexes . .6 IV. Reaction Possibilities of Carbene Complexes . .8 V. Transition Metal-Carbyne Complexes . 21 VI . Reaction of Other Peptacarbonylcarbene Complexes with Boron Trihalides . 24 VII. Reaction of Pentacarbonylcarbene Complexes with Halides of Aluminum and Gallium . 27 VIII. Reaction of Lithium Benzoylpentacarbonyltungstate with Triphenyldibromophosphorane . 27 IX. Reactivity of the Carbyne Ligarid . 28 References . 29 Coordination of Unsaturated Molecules to Transition Metals STEVEN D. ITTEL and JAMES A. IBERS I. Introduction . 33 11. Theoretical Models . 35 111. Structural Results . 37 IV. Summary . 59 References . 60 Methyltin Halides and Their Molecular Complexes V. S. PETROSYAN, N. S. YASHINA, and 0. A. REUTOV I. Introduction . 63 11. Methods of Study . 64 111. Structures of Methyltin Halides . 68 IV. Molecular Complexes of Methyltin Halides . 76 V. Conclusion . 91 References . 92 V vi CONTENTS Chemistry of Carbon-Functional Alkylidynetricobalt Nonacarbonyl Cluster Complexes DIETMAR SEY FERTH I. Introduction : General Properties of Alkylidynetricobalt Nonacarbonyl Complexes . 98 11. Synthesis of Alkylidynetricobalt Nonacarbonyl Complexes . 100 111. Chemistry of the Trirobaltcarbon Decacnrbonyl Cation . 110 Iv. Highly Stable Nonacarbonyl Tricobaltcarbon-Substituted Carbonium Ions . 119 v. Decomposition Reactions and Derived Synthetic Applications of Alkylidynetricobalt Konacarbonyl Complexes . 135 VI. Concluding Remarks . 138 References . 141 Ten Years of Metallocarboranes KENNETH P. CALLAHAN and M. FREDERICK HAWTHORNE I. Introduction . 145 11. Metallocarboranes: Synthetic Methods , . 150 111. Twelve-Vertex Metallocarboranes . 155 IV. Thirteen-Vertex Metallocarboranes . 167 V. Fourteen-Vertex Metallocarboranes . 171 VI. Eleven-Vertex hletallocarboranes . 171 VII. Ten-Vertex Metallocarboranes . 175 VIII. Nine-Vertex Metallocarboranes . 178 IX. Oxidative Addition to B-H Bonds . 180 X. Metallocarboranes in Homogeneous Catalysis . 182 References . 183 Recent Advances in Organoantimony Chemistry ROKURO OKAWARA and YOSHIO MATSUMURA I. Introduction . 187 11. Hexacoordinate Mono- and Diorganoantimony Compounds . 188 111. Triorganostibine Sulfide . 192 IV. Tertiary Stibines . 197 References . 202 Pentaalkyls and Alkylidene Trialkyls of the Group V. Elements HUBERT SCHMIDBAUR I. Introduction . 205 11. Simple Nitrogen Ylides . 207 CONTENTS vii 111. Phosphorus Ylides and Pentaalkylphosphoranes . 209 IV. Arsenic Ylides and Pentaalkylarsoranes . 224 V. Antimony Ylides and Pentaalkylstiboranes . 23 1 VI. Bismuth Compounds . 236 VII. Related Compounds of Vanadium, Niobium, and Tantalum . 236 References . 240 Acetylene and Allene Complexes: Their Implication in Homogeneous Catalysis SEI OTSUKA and AKIRA NAKAMURA I. Introduction . 245 11. Acetylene Complexes. 246 111. Allene Complexes . 265 References . 279 High Nuclearity Metal Carbonyl Clusters P. CHINI, G. LONGONI, and V. G. ALBANO I. Introduction . 285 11. Structural Data in the Solid State . 286 111. Structural Data in Solution . 306 IV. Syntheses. 311 V. Methods of Separation . 316 VI . Reactivity . 317 VII. Iron Derivatives . 323 VIII. Ruthenium Derivatives , 324 IX. Osmium Derivatives . 325 X. Cobalt Derivatives , 325 XI. Rhodium Derivatives . 327 XII. Iridium Derivatives . 332 XIII. Nickel Derivatives . 333 XIV. Platinum Derivatives . 334 xv. Bonding Theories . 336 References . 34 1 Free Radicals in Organometallic Chemistry M. F. LAPPERT and P. W. LEDNOR I. Introduction . 345 11. Metal-Centered Organometallic Radicals . 349 111. Other Organometallic Radicals . 367 IV. Bimolecular Homolytic Substitution (SH~)at the Metal Center of an Organometallic Substrate . 370 viii CONTENTS V. Addition or Elimination Radical Reactions , . 381 VI. Appendix . 390 References . 392 SUBJECTINDEX . 401 CUMULATIVELIST OF CONTRIBUTORS . 410 CUMULATIVELIST OF TITLES , . 412 fist of Contributors Numbers in parentheses indicate the pages on which the authors’ contributions begin. V. G. ALBANO(ass), Istiticto de Chtmicu Generale dell’ Universitd, Milano, Italy KENNETH1’. CALLAHAN(143), Metcalj Research Laboratory, Department of Chemistry, Brown University, Providence, Rhode Island P. CHINI(as,;), Istituto de Chirnica Generale dell’ Universitd, Milano, Italy ERNST OTTO FISCHER(1), Inorganic Chemistry Laboratory, Technical University, Munich, West Germany M. FREDERICKHAWTHORNE (143), Department of Chemistry, University of California, Los Angeles, Caltjornia JAMESA. IBERS(33), Depnrtntent oj Chemistry, Northwestern University, Evanston, Illinois STEVEND. ITTEL(33), Central Research and Development Department, E. I. du Pont de Nemours and (’onipany, Wilmington, Delaware M. F. LAPPERT(345), School of Molecular Sciences, University of Sussex, Brighton, England P. W. LEDNOR*(345), School of Molecular Sciences, University of Sussex, Brighton, England G. LONGONI(ass), Istituto de Chiniica Generale dell’ Universitd, Milano, Italy YOSHIOMATbUMURAt (187), Department of Applied Chemistry, Osaka University, Yamadakartzi, Suita, Osaka, Japan AKIRA NAKAliURA (24,5), Department of Chemistry, Faculty of Engineering Science, Osaka Universit!y, Toyonaka, Osaka, Japan ROKUROOKAWARA (187), Department of Applied Chemistry, Osaka Uni- versity, Yamadakami, Suita, Osaka, Japan * Present address: Institut fur Anorganische Chemie der Universitat Munchen, 8 Miinchen 2, Meiserstrasse 1, Germany. t Present address: Japan Synthetic Rubber Co., Ltd., Research Laboratory, 7569 Ikuta, Tama, Kawasaki, Japan. ix X LIST OF CONTRIBUTORS SEI OTSUKA(245), Department of Chemistry, Faculty of Engineering Science, Osaka University, Toyonaka, Osaka, Japan V. S. PETROSYAN(63), Chemistry Department, M. 8. Lomonosov Moscow State University, MOSCOW,USSR 0. A. REUTOV(63), Cheniistry Department, M.V. Lomonosov Moscow State University, MOSCOW,USSR HUBERTScmmBAm (205), Anorganisch-chemisches Laboratorium, Tech- nische Universitat Munchen, Munich, West Germany DIETIIARSEYFEwrn (97), Department of Chemistry, Massachusetts Institute oj Technology, Cambridge, Massachusetts N. S. YAsnIxA (63), Chemistry Department, M.V. Lomonosov Moscow State University, Moscow , USSR Preface The first volume of Advances in Organometallic Chemistry was published early in 1964, and twelve other volumes have appeared since that date. The Editors have sought to produce a series of books containing specialist articles on all aspects of this field. The success of the series, as judged by the reviews of the books published in the journal literature, is due in large measure to the cooperation and help we have received from some one hundred and ten contributors. However, the demand for authoritative surveys of topics in organometallic chemistry derives mainly from the continued resilience of this area of endeavor, one measure of which is the annual appearance of over 2000 primary journal articles. After a little over a decade of publication it seemed to the Editors that we should arrange for the appearance of a commemorative Volume con- taining articles by distinguished chemists which would emphasize both the wide scope of organometallic chemistry and its international character. The number of contributors was necessarily limited by the need to keep the book to a reasonable length. This presented a problem in relation to selection of authors. Our choice is, therefore, a personal one guided to some degree by geographical distribution and the desire to balance transition metal chemistry versus main group metal chemistry. F. G. A. STONE It. WEST xi This Page Intentionally Left Blank Advances in ORGANOMETALLIC CHEMISTRY VOLUME 14 This Page Intentionally Left Blank On the Way to Carbene and Carbyne Complexes* ERNST OTTO FISCHER fnorganic Chemistry labardory Technical University Munich, West Germoqy I. Introduction . 11. Transition Metal-Carbene Complexes . A. Preparation of the First Carbene Complexes . B. Bonding Concepts and Spectroscopic Findings . 111. Other Syntheses of Carbene Complexes . IV. Reaction Possibilities of Carbene Complexes . A. Addition and CO Substitution . B. Transition Metal-Carbene Complex Residues aa
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