The chemistry of the metal-carbon bond. V.2. The nature and cleavage of metal-carbon bonds

910 Pages·20.149 MB·English

by  Hartley F.R., Patai S. (eds.)

The Chemistry of the Mctal-Carbon Bond, Volume 2
Edited by F. R. Hartley and S. Patai
01 985 John Wiley & Sons Ltd
The chemistry of the
Volume 2
The nature and cleavage of
metal-carbon bonds
Edited b y
FRANK R. HARTLEY
The Royal Military College of Science
Sliriuetz h am, England
and
SAUL PATAI
The Hebrew Uniuersity
Jerusalem, Israel
1985
JOHN WILEY & SONS
CHICHESTER-NEW YORK-B RISB AN E-TORONTO-SING APORE
An Interscience @ Publication
Copyright @ 1985 by John Wiley & Sons Ltd.
All rights reserved
No part of this book may be reproduced by any means,
nor transmitted, nor translated into a machine language
without the written permission of the publisher.
Library of Congress Cataloging in Publication Data
Main entry under title:
The Nature and cleavage of metal-cnrbon bonds.
(The Chemistry of the metalkcarbon bond; v. 2)
(The Chemistry of functional groups)
'An Interscience publication.'
Includes indexes.
1. Organometallic compounds. 2. Chemical bonds.
I. I-lartley, F. R. 11. Patai, Saul. 111. Series.
IV. Series: Chemistry of functional groups.
QD410.C43 1984 vol. 2 547'35s [547'.05] 83-145(i.1
[QD4111
British Library Cataloguing in Publication Data
The Chemistry of the metal-carbon bond.-
(The chemistry of functional groups)
Vol. 2: The nature and cleavage of metal-carbon bonds
1. Organometallic compound
I. I-lartley, Frank 11. Patai, Saul
111. Series
547l.05 QD41 I
ISBN 0 471 00282 9
Filmset and printed in Northern Ireland by The Universities Press (Belfast) Ltd.,
and bound by the Pitman Press, Bath, Avon.
VQIU~T2W-C ontributing authors
Michael H. Abraham Chemistry Dcpartment, University of Surrey, Guildford,
Surrey GU2 5XH, UK
John J. Alexander Department of Chemistry, University of Cincinnati, Cin-
cinnati, Ohio 45221, USA
Philip J. Barker Research School of Chemistry, Australian National Uni-
versity, P.O. Box 4, Canberra, A.C.T. 2600, Australia
J. Cross Chemistry Department, The University, G1asgow GI2
Ron
SQQ, Scotland, UK
Priscilla Grellier Chcmistry Dcpartment, University of Surrey, Guildford,
L.
Surrey GU2 5XH, UK
Louis S. Hegedus Department of Chemistry, Colorado Statc University,
Fort Collins, Colorado 80523, USA
Mike D. Johnson Dcpartmcnt of Chemistry, University College London,
20 Gordon Street, London WClH OAJ, UK
John P. Oliver Department of Chemistry, Wayne State University, De-
troit, Michigan 48202, USA
Eric S. Paterson Dcpartment of Chemistry, University of Aberdeen, Mes-
ton Walk, Old Aberdcen AB9 2UE, Scotland, UK
Chris J. Pickett ARC Unit of Nitrogen Fixation, University of Sussex,
Brighton, East Sussex BN1 9RQ, UK
John K. Stille Department of Chemistry, Colorado Statc University,
Fort Collins, Colorado 80523, USA
Jim Wardell Department of Chemistry, University of Aberdeen, Mes-
L.
ton Walk, Old Aberdeen AH9 2UE, Scotland, UK
Jeremy N. Winter Department of Chemistry, University of York, Hesling-
ton, York YO1 5DD, UK
V
The Chemistry of the MetuI-Carbon Bond is a multi-volume work within the well
established series of books covering The Chemistry of Functional Groups. It aims to
cover the chemistry of the mctal-carbon bond as a whole, but lays emphasis on the
carbon end. It should therefore be of particular interest to thc organic chemist. The
gcneral plan of the matcrial will be the same as in previous books in thc series with
the exception that, because of the large amount of material involved, this will be a
multi-volume work. The first volume was concerned with:
(a) Structure and thermochemistry of organomctallic compounds.
(h) Thc preparation of organometallic compounds.
(c) The analysis and spectroscopic characterization of organometallic compounds.
The present volume is concerned with clcavage of the metal-carbon bond. It also
includes the chaptcr on the structure and bonding of main group organometallic
compounds dcferred from the first volume. The chapter on the photochemical
cleavage of metal-carbon bonds has not yct been completed and will be included in
a later volume. Subsequent volumes will be concerned with the use of organomctallic
compounds for the formation of new carbon-carbon, carbon-hydrogen, and
othcr carbon-element bonds. In classifying organomctallic conipounds we havc
used Cotton’s hapto-norncnclature (q -) to indicatc tlic number of carbon atoms
directly linked to a single metal atom.
In common with other volumes in The Chemistry of ihe Fzirzctional Groups series,
the emphasis is laid on the functional group treated and on the effects which it exerts
on the chemical and physical properties, primarily in the immediate vicinity of the
group in qucstion, and sccondarily on the behaviour of the wholc molecule. The
coveragc is restrictcd in that material included in easily and generally available
secondary or tertiary sources, such as Clteinical Reuiews and various ‘Advances’ and
‘Progrcss’ scries as well as textbooks (i.e. in books which are usually found in the
chemical libraries of univcrsities and rcsearch institutes) is not, as a rule, repeated in
detail, unless it is necessary for the balanced treatment of the subject. Thercforc,
each of the authors has bcen asked not to give an cncyclopaedic covcrage of his
subjcct, but to concentrate on the most important reccnt devclopments and mainly
on material that has not been adcquately covercd by reviews or other sccondary
sources by the time of writing of the chapter, and to address himself to a reader who
is assumed to be at ii fairly advanced postgraduate level. With these rcstrictions, it is
realised that no plan can be deviscd for ii volume that would give a complete
covcragc of the subject with no ovcrlnp between the chapters, while at the samc timc
preserving the readability of the text. The Editors set thcmselves the goal of attaining
reasonable coverage with moderate overlap, with a minimum of cross-refercnces
between the chapters of each volume. In ihis manner sufIicicnt freedom is givcn to
each author to producc readable quasi-monographic chapters. Such a plan necessar-
ily means that the breadth, dcpth and thought-provoking nature of each chapter will
ciiffer with the views and inclinations of the author.
The publication of the Functional Group Series would never havc started without
the support of many people. Foremost among thcse is Dr Arnold Weissbcrgcr,
whose reassurance ancl trust encouraged the start of the task and who continues to
vii
viii Foreword
help and advise. This volume would never have reached fruition without Mrs
Trembath’s and Mrs Baylis’s help with typing and the efficient and patient coopera-
tion of several staff members of thc Publisher, whose code of ethics does not allow us
to thank them by name. Many our colleagues in England, Israel and elsewhere
of
gave help in solving many problems, especially Profcssor Z. Rappoport. Finally, that
the project ever reached completion is due to the essential support and partnership
of our wives and families.
FRANK HARTLEY
Shrivenham, England
SAUL PATAI
Jerusalem, Israel
contents
1. Electrochemical cleavage metal-carbon bonds 1
of
C. Pickett
J.
2. Heterolytic cleavage of main group metal-carbon bonds 25
M. H. Abraham and P. L. Grellier
Homolytic cleavage metal-carbon bonds: Groups I to V 151
3. of
P. J. Barker and J. N. Winter
4. Insertions into main group metal-carbon bonds 21
9
J. L. Wardell and E. S. Paterson
5. insertions into transition metal-carbon bonds
339
J. J. Alexander
6. Nucleophilic attack on transition metal organometallic compounds 40 1
L. S. Hegedus
7. Electrophilic attack on transition metal p’-organometallic com-
pounds 513
M. D. Johnson
8. Transition metal-carbon bond cleavage through P-hydrogen elimi-
nation 559
J. Cross
R.
Oxidative addition and reductive elimination 625
9.
J. K. Stille
10. Structure and bonding of main group organometallic compounds 789
J. P. Oliver
Author index 827
Subject index 887
ix
List of Abbaewiatisns Used
A appearance potential
acac acetylacetonc
ac acrylonitrile
acacen bis(acetylacetonate)ethylenedianiinc
aibn azobisisobutyronitrile
all ally1
An actinide metal
aP antiplanar
aPPe Ph2AsCHZCHzPPh2
bae
bis(acetylacetonate)ethylcnediamine
biPY 2,2'-bipyridyl
cd circular dichrosim
cdt
E,E,E-cyclododeca-l,5,9-triene
cht cyclohcptatriene
CI chemical ionization
CIDNP chemically induced dynamic nuclear polarization
CNDO complete neglect of differcntial overlap
coct cyclooctene
cod cycloocta-l,5-diene
cot cyclooctatetraene
CP 3 '-cyclopentadienyl
CP" ?'-pentamethylcyclopentadienyl
C.P. cross-polarization
CY cyclohcxyl
dba dibenzylideneacetone
dbn 1
,S-diazabicyclo[5.4.O]non-5-cne
dbu
1,8-diazabicyclo[5.4.0]undec-7-enc
dccd dicylohexylcarbodiiniide
def diethyl fumarate
diars o-bis(dimethylarsin0)benzene
dibah diisobutylaluminium hydride
diop
2,3-o-isopropylidene-2,3-dihydroxy1-, 4-bis(diphenyIphosphino)butane
dme 1,2-dimethoxyethane
dmf dimethylformamide
dmfm dimethyl fumarate
dmm dimethyl malente
dmpe bis( 1,2-diniethylphosphino)eth:in~
dotnH
bis(diecetylmonoxime)propylene-l,3-diamine
dPm dipivaloylmethanato
dPPb his( 1,4-diphenyIphosphino)butane
dPPc bis( 1,2-~1iphenylphosphino)ethane
dPPm bis(1 ,1-diphenylphosphino)methanc
xi
xii List of abbreviations uscd
dPPP bis( 1,3-diphenylpIiosphino)propane
dmso dirnethyl sulphoxide
half-wave potential
E1,2
ecc electron transfer+hernical step-further electron transfer
cc enantiomcric excess
EI electron impact
E” peak potential
ESCA electron spcctroscopy for chemical analysis
eV electronvolt
Fc ferrocene
FD field desorption
FI field ionization
fnin fumaronitrile
fod F,C(CF,),COCH=C(0)CMe3
FP Fc(5~-C sHs)(CO)~
FPz: F c (5~-C s~~s)(CO)(PPhJ
FT Fourier transform
h fac hexafluoroacctonc
hfacac hcxafluoroacetylacetonato
hmdb
licxamcthyl(Dewar)benzenc
hmpa hcxamctli ylphosplioramidc
hmpt hexamet hylphosphorotriamide
HOMO highest occupied molecular orbital
1 ionization potential
ICR ion cyclotron resonance
ionization potential
INDOR inter-nuclear double resonmcc
LCAO linear combination of atomic orbitals
Ida lithium diisopropylamide
Ln lanthanide metal
LUMO lowcst unoccupied rnolccular orbital
M nictal
M parcnt molecule
ma malcic anhydride
MAS magic angle spinning
171 -cpba ni -chloroperbenzoic acid
modificd ncglcct of diatomic overlap
MNDO
map 2-methyl-2-nitrosopropane
ni millisecond
s
nbd norborna-l,5dicnc
nbs N-bromosuccinimide
nmP N-methylpyr-rolidone
oA o -allylphenyldinietliylarsine
Pe pentenyl
phen o-phcnanthroline
pmdetn Pen tamethyldiethylenetriaminc
...
List of abbreviations used
Xlll
PPm parts per million
PRDDO partial retention of diatomic diffcrcntial overlap
psi pounds per squarc inch
PY pyridyl
PZ pyrazol yl
RT room tcmperature
salen
bis(sa1icylaldehyde)ethylenediamine
salophen
bis(salicyla1dehyde)-o-phenglenediaminc
SCE Saturated calomel electrode
set singlc electron transfer
SOMO singly occupied molccular orbital
SP synplanar
SPT selective population transfer
tba
tribenzylideneacetylacetone
tcne tetracyanoeth ylene
thf tctrah ydrofuran
tmeda tetramethyleth ylcncdiamine
tms tetramethylsilanc (only used in this context as a free standing symbol)
tms trimethylsilyl (only used in this context either with a dash after it or
adjacent to a chemical symbol)
tond
1,3,5,7-tetramethyl-2,6,9-trioxobicyclo[3.3.1]nona-3,7-dicnc
t 0s tosyl
ttfa thallium tristrifluoroncctatc
un olefin or acetylene
X halide
The Chemistry of the Mctal-Carbon Bond, Volume 2
Edited by F. R. Hartley and S. Patai
01 985 John Wiley & Sons Ltd
CHAPTER 1
Electrochemical cleavage of
rn etaI -ca rbon bonds
C. J. PICKET
ARC Unit of Nitrogen Fixation, University of Sussex, Brighton, East
Sussex BN7 9RQ, UK
I. INTRODUCTION 1
11. THE METAGCARBON SIGMA BOND . 2
A. Introduction . 2
B. Main Group . 2
1. Oxidation . 2
a. Mechanisms . 2
b. Organic products . 4
2. Reduction . 7
a. Mechanisms and products . 7
C. Transition Metal Alkyls, Aryls, and Acyls 11
Introduction 11
1.
2. Reduction . 11
3. Oxidation of transition metal alkyls, aryls and acyls 14
111. T-BONDED HYDROCARBON LIGANDS
15
IV. TRANSITION METAL CARBONYL, CARBENE, CARBYNE, AND
ISOCYANIDE COMPLEXES 18
A. Introduction . 18
B. Oxidation . 18
C. Reduction . 20
V. CONCLUSIONS . 21
VI. ACKNOWLEDGEMENTS . 22
VII. REFERENCES . 22
1. INTRODUCTION
Elcctron-transfer reactions of organometallic compounds can be studied in great
detail by thc application of modern elcctrochemical methods. Thermodynamic data
can be obtained, products prepared by electrosynthesis, unstable intcrmediatcs
generatcd, and their decay rates or spectroscopic properties measured. Tn addition,
rates of heterogeneous electron transfer froni or to a substrate in solution can bc
estimatcd and adsorption phenomena studied.
1