Transition Metal Carbyne Complexes

273 Pages·1993·22.09 MB·English

by  R. R. Schrock, R. Toreki, G. A. Vaughan, A. Farooq (auth.), F. R. Kreißl (eds.)

Transition Metal Carbyne Complexes
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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-
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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 CYCLIZAT IONS 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-
CYA NIDE-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 DETERMINAn ON OF THE CHEMICAL BONDS IN SOME META L-
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