Table Of ContentOrganometallic Compounds 1
Editor.
Michael Dub
Compounds of Transition
Metals
Covering the Literature from 1937 to 1964
Second Edition
Volume
I
COMPOUNDS OF TRANSITION METALS
ORGANOMETALLIC COMPOUNDS
METHODS OF SYNTHESIS
PHYSICAL CONSTANTS AND CHEMICAL REACTIONS
Volume r
COMPOUNDS OF TRANSITION METALS
Second Edition
Covering the Literature from 19 3 7 to 1964
Edited by
MrcHAEL DuB
Central Research Department, Monsanto Company
Springer Science+Business Media, LLC
1966
ORGANOMETALLIC COMPOUNDS
Second Edition
In preparation
Voi. II -Compounds of Germanium, Tin and Lead
by Richard W. W eiss
Voi. III-Compounds of Arsenic, Antimony, and Bismuth
by Michael Dub
ISBN 978-3-642-52103-4 ISBN 978-3-642-52101-0 (eBook)
DOI 10.1007/978-3-642-52101-0
Ali righcs reserved, especially chat of cranslacion into foreign languages
It is also forbidden ta reproduce chis book, either whole or in part, by phoromechanical means
( photostat, microfilm and/ or microcard or any other means)
wichouc written permission from che Publishers
© 1966 by Springer Science+Business Media New York
Originally published by Springer-Verlag New York, Inc. in 1966
Library of Congress Catalog Card Number 66-28249
Tide No. 4357
PREP ACE TO THE SECOND EDITION
The aim of this Compilation has been to provide a comprehensive, non
critical source of information concerning organometallic compounds. The
scope is limited to the compounds containing at least one carbon-metal
bond. The information includes methods of preparation, properties,
chemical reactions and applications.
The First Edition comprised the literature from 1937 to 1958. The Second
Edition is completely revised and extended through 1964. The literature
prior to 1937 was thoroughly covered by E. Krause and A. von Grosse in
"Die Chemie der metall-organischen Verbindungen, 11 Verlag von Gebrueder.
Borntraeger, Berlin, 1937.
Our work consists of three volumes. Volume I contains derivatives of the
transition metals of Groups III through VIII of the Periodic Table. Volume
II contains derivatives of germanium, tin and lead. Volume III contains
derivatives of arsenic, antimony and bismuth.
The Compilation is based on searches through Chemical Abstracts. The
collection of references for 1964 was completed before the Subject Indexes
to Volumes 60 and 61 of the Abstracts were available; thus some omissions
in the coverage of that year are possible.
We have attempted to make the coverage of the literature complete in
order that the Compilation may have best utility to the chemist, chemical
engineer, patent attorney and editor. In the interest of brevity, certain
numerical data are omitted, but references to the original literature are
given. Yield data are rounded to two significant figures. Wherever
possible, tables have been used. The entries in the Bibliography section
include references to Chemical Abstracts.
I am indebted to Dr. R. S. Gordon, Director of the Central Research
Department, and to Mr. W. A. Wilkinson, Head of the Information Center,
Monsanto Company, for their generous support of this project. I am also
indebted to Dr. R. w. Weiss, the Coeditor of Volume II, for his invaluable
advice on the form of this Compilation. My thanks are due to the library
staff at the Information Center for their assistance and especially to
Mrs. Mary Alice Doiron for the preparation of the typescript for the
photo-offset printing.
Michael Dub
St. Louis, Missouri
January 1966
III
INTRODUCTION TO VOLUME 1
This volume covers derivatives of the transition metals of Groups III
through VIII of the Periodic Table, in which organic radicals and/or
aromatic, cyclomatic, olefinic, acetylenic and organa-isocyanide ligands
form a- and/or n-bonds with the metal atoms. Metal carbonyls and cyanides
and salts with cyanometal anions, as such, are not considered.
Most of the transition metals form compounds with the cyclopentadienyl
moiety bonded to the metal atoms by means of three n-electron pairs. It
is understood that all cyclopentadienyl derivatives in this volume contain
the five-membered ring n-bonded to the transition metals, unless a a
bonding is indicated or suggested.
To facilitate the use of the compilation and a correlation of analogous
types of organic derivatives of different transition metals, the infor
mation on the individual metals is arranged and numbered as follows:
1. a-Bonded derivatives, except for the a-cyclopentadienyl compounds;
2. Cyclopentadienyl derivatives;
3· n-Allyl derivatives and analogs;
4. n-Complexes with aromatic ligands;
5. n-Complexes with olefinic compounds, including cyclic compounds
with olefinic bonds;
6. n-Complexes with acetylenic compounds;
7. n-Complexes with organo-isocyanides;
8. Organobimetallic compounds, including boron and silicon derivatives.
Further subdivisions of the main classes are obvious from the Table of
Contents. For the convenience of arranging certain types of compounds
which are peculiar to a particular metal or to a few metals, 90 through
99 subclass numbering is used.
A Supplement, pages 735 through 747, includes a few compounds omitted
from the data sections and Tables 12, 13, 14 and 16, which were transferred
to pages 736, 742, 743 and 745, respectively, due to certain rearrangements
made within the first hundred pages of the typescript. Crossreferences to
these entries are given in the appropriate sections.
Michael Dub
v
ABBREVIATIONS
The following abbreviations are used in addition to, or at variance
with, those in Chemical Abstracts:
BiPy bipyridyl
corr. corresponding
dec. decomposition, decomposes, decomposed, decomposing
DMF dimethylformamide
Fe ferrocenyl radical, CsHsFeCsH4-
Fed l,l1-ferrocenylene biradical, -CsH4FeCsH4-
GLC gas-liquid chromatography
IR infrared
liq. liquid (adjective)
m. melting point, melts at, melted at
M a metal atom in generic formulae
matl. material(s)
obtd. obtained
Pip piperidine
prod. product( s)
psi pound per square inch pressure
Py pyridine
ref. reference(s)
r. t. room temperature
rxn. reaction{s)
subl. Sublimes at, sublimed at, sublimation
substd. substituted
THF tetrahydrofuran
TLC thin-layer chromatography
UV ultraviolet
VI
CONTENTS
PREFACE TO THE SECOND EDITION III
INTRODUCTION TO VOLUME I v
ABBREVIATIONS VI
GROUP III METALS
INCLUDING LANTHANIDES AND ACTINIDES
1. Alkyl Derivatives 1
2.1 Monocyclopentadienyl Derivatives 1
2.2 Biscyclopentadienyl Derivatives 2
2.3 Tricyclopentadienyl Derivatives 3
2.4 Tetracyclopentadienyl Derivatives 4
GROUP IV METALS
TIT&~IUM COMPOUNDS
1.91 Alkyl and Aryl Derivatives of Divalent Titanium 5
1.92 Alkyl and Aryl Derivatives of Trivalent Titanium 5
1.93 Alkyl and Aryl Derivatives of Tetravalent Titanium 6
2. Cyclopentadienyl Derivatives and Analogs 10
2.1 Monocyclopentadienyl Derivatives 10
2.1.91 Compounds of Doubly Connected Titanium 10
2 .1.92 Compounds of Triply Connected Titanium 11
2.1.93 Compounds of Quadruply Connected Titanium 11
2 .1.93.1 Trialkyl and Triaryl Derivatives 11
2 .1.93.2 The Halides 12
2.1.93.4 The Alkoxides, Hydroxides and Carboxylates 15
2.1.94 Compound of Quintuply Connected Titanium 17
2.2 Biscyclopentadienyl Derivatives 17
2.2.91 Compound of Doubly Connected Titanium 17
2.2.92 Compounds of Triply Connected Titanium 17
2.2.93 Compounds of Quadruply Connected Titanium 19
2.2.93.1 Hydrocarbyl Derivatives 19
2.2.93.2 The Halides 22
2.2.93.4 The Alkoxides and Carboxylates 29
2.2.93.5 Thio Derivatives 30
2.2.93.9 Miscellaneous Derivatives 30
2.3 Tricyclopentadienyl Derivative 30
2.4 Tetracyclopentadienyl Derivative 31
VII
4. Arene Derivatives 31
5. Complexes with Olefins 31
5.2 Cyclic Derivatives 31
8. Bimetallic Compounds 31
8.3 Complexes with Aluminum 31
8.4 Complexes with Silicon, Germanium and Lead 34
ZIRCONIUM COMPOUNDS
1.1 Alkyl Derivatives
2. Cyclopentadienyl Derivatives and Analogs
2.1 Monocyclopentadienyl Derivatives
2.1.9 Cyclopentadienylene Derivatives
2.2 Biscyclopentadienyl Derivatives
4. Arene Derivative
8. Bimetallic Compounds
HAFNIUM COMPOUNDS
2. Cyclopentadienyl Derivatives 42
8. Bimetallic Compounds 42
GROUP V METALS
VANADIUM COMPOUNDS
l. Alkyl and Aryl Derivatives 43
2. Cyclopentadienyl Derivatives 43
2.1 Monocyclopentadienyl Derivatives 43
2.1.91 Compounds of Doubly Connected Vanadium 43
2.1.93 Compounds of Quadruply Connected Vanadium 43
2.1.94 Compounds of Quintuply Connected Vanadium 44
2.1.95 Compounds of Sextuply Connected Vanadium 46
2.2 Biscyclopentadienyl Derivatives 46
2.2.91 Compounds of Doubly Connected Vanadium 46
2.2.92 Compounds of Triply Connected Vanadium 47
2.2.93 Compounds of Quadruply Connected Vanadium 48
2.2.94 Compounds of Quintuply Connected Vanadium 49
3. Cycloheptatrienyl Derivatives 49
4. Arene Derivatives 50
5. Complexes with Olefins 52
8. Bimetallic Compounds 52
NIOBIUM COMPOUNDS
2. Cyclopentadienyl Derivatives 52
2.1 Monocyclopentadienyl Derivatives 52
2.2 Biscyclopentadienyl Derivatives 52
2.4 Tetracyclopentadienyl Derivative 53
VIII
TANTALUM COMPOUNDS
1. Alkyl and Aryl Derivatives 53
2. Cyclopentadieny1 Derivatives 53
4. Arene Derivatives 54
8. Bimetallic Compounds 54
GROUP VI METALS
CHROMIUM COMPOUNDS
1. Alkyl, Aralkyl, Alkynyl and Aryl Derivatives 55
2. Cyc1opentadienyl Derivatives and Analogs 59
2.1 Monocyc1opentadienyl Derivatives 59
2.1.2 The Halides 59
2.1.4 The Carbonyls and Oxide 61
2 .1. 5 The Thio Derivatives 63
2.1.6 The Nitrosyls 63
2.1.9 Miscellaneous Monocyclopentadienyl Derivatives 65
2.2 Biscyclopentadienyl Derivatives and Analogs 67
2.3 Tricyclopentadienyl Derivative 69
3· n-Allyl Derivative 69
4. Arene Derivatives 69
4.1 Monoarene Tricarbonyl Derivatives 69
4.1.91 Dinuclear Complexes 75
4.1.92 Dicarbonyl Complexes with Miscellaneous Ligands 75
4.1.93 Miscellaneous Monoarene Derivatives 75
4.2 Bisarene Derivatives and Cr(I) Salts 76
4.2.91 Symmetrical Compounds 76
4.2.92 Nonsymmetrical Compounds 86
5· Complexes with Olefins 89
5.1 Aliphatic Derivatives 89
5.2 Cyclic Derivatives 89
7. Complexes with Isocyanides 92
8. Bimetallic Compounds 93
MOLYBDENUM COMPOUNDS
1. Alkynyl and Aryl Derivatives 95
2. Cyclopentadienyl Derivatives 95
2.1 Monocyclopentadienyl Derivatives 95
2.1.91 The CsHsMo(CO)sR and CsHsMo(CO)s-nLnX Type Compounds 95
2.1.92 The [CsHsMo(C0)4-nLn]X Compounds 98
2.1.93 Dimeric Compounds 99
2 .1.94 Alkyne-, P-, As- and S-Bridged Compounds 101
2.1.95 Miscellaneous Compounds 102
2.2 Biscyclopentadienyl Derivatives and Analogs 105
2.4 Tetracyclopentadienyl Derivative 106
3· n-Allyl Derivative 106
IX
