Table Of ContentOrganometallic Compounds of the
Lanthanides, Actinides and
Early Transition Metals
Organometallic Compounds of the
Lanthanides,
Actinides and Early
Transition Metals
Edited by
D. J. Cardin
Trinity College, Dublin
S. A. Cotton
Stanground School, Peterborough
M. Green
University of Bristol
J. A. Labinger
Atlantic Richfield Company
Chatsworth, California
SPRINGER-SCIENCE+BUSINESS MEDIA, B.V.
ISBN 978-0-412-26830-4
© 1985 Springer Science+Business Media Dordrecht
Originally published by Chapman and Hali Ltd in 1985
All rights reserved. No part of this book may be reprinted, or reproduced or
utilized in any form by any electronic, mechanical or other means, now known or
hereafter invented, including photocopying and recording, or in any information
storage or retrieval system, without permission in writing from
Springer-Science+Business Media. B.V.
Library of Congress Cataloging in
Publication Data
Main entry under title:
Organometallic compounds of the
lanthanides, actinides, and early transition
metals.
lncludes index.
1. Organometallic compounds
Handbooks, manuals, etc.
2. Rare earth metal compounds British Library Cataloguing in
Handbooks, manuals, etc. Publication Data
3. Actinide elements-Handbooks, Organometallic compounds of the
manuals, etc. lanthanides, actinides and early transition
4. Transition metal compounds metals.
Handbooks, manuals, etc.
1. Cardin, D. J., 1941- . Il. Series. 1. Organometallic compounds 2. Rare
QD411.'73 1985 547'.054 84-29363 earth metal compounds 3. Actinide
elements
1. Cardin, D.J.
547' .054 QD4ll
ISBN 978-0-412-26830-4
ISBN 978-0-412-26830-4 ISBN 978-1-4899-7164-7 (eBook)
DOI 10.1007/978-1-4899-7164-7
Contents
Preface pagevn
Introduction
IX
Am Americium 1
Bk Berkelium 3
Ce Cerium 5
Cf Californium 8
Cm Curium 10
Cr Chromium 12
Dy Dysprosium 40
Er Erbium 42
Eu Europium 46
Gd Gadolinium 48
Hf Hafnium 51
Ho Holmium 61
La Lanthanum 63
Lu Lutetium 65
Mn Manganese 70
Mo Molybdenum 93
Nb Niobium 118
Nd Neodymium 127
Np Neptunium 130
Pa Protactinium 132
Pm Promethium 134
Pr Praseodymium 136
Pu Plutonium 138
Re Rhenium 140
Sc Scandium 156
v
Contents
Sm Samarium 159
Ta Tantalum 163
Tb Terbium 171
Tc Technetium 173
Th Thorium 176
Ti Titanium 185
Tm Thulium 211
u Uranium 213
v
Vanadium 229
w Tungsten 250
y Yttrium 275
Yb Ytterbium 279
Zr Zirconium 287
Name Index 309
Molecular Formula Index 337
CAS Registry Number Index 379
vi
Preface
This is one of the first volumes to be published in the series of Chapman and Hall
Chemistry Sourcebooks which provides carefully tailored information to workers in
specialized areas of chemistry. The information contained in this book is derived from the
Dictionary of Organometallic Compounds, published in November 1984.
The wide range of metals in this particular volume is of great interest to inorganic and
organic chemists alike. Organic derivatives of several of the early transition elements are
involved in commercial catalytic processes, particularly important examples being the use
of titanium compounds in Ziegler-Natta polymerisation and molybdenum and tungsten
intermediates in alkene metathesis. Reactions involving the organolanthanides and
organoactinides have as yet been less well explored, but there is burgeoning interest in
their synthesis. The large variety of compounds in this particular compendium will
ensure its appeal to a wide readership.
The databank on the properties of organometallic compounds, which is represented in
its current form by the Dictionary of Organometallic Compounds and its subset
publications such as this volume, will be kept continuously up-to-date. Supplements to the
main Dictionary will appear annually and revised editions of this Sourcebook will be
published from time to time as demands permits.
D.J. Cardin
S.A. Cotton
M.Green
J .A. Labinger
vii
This Sourcebook has been reproduced in part from the
Dictionary of Organometallic Compounds. If you find it
useful and you would like full coverage, then why not buy
the Main Work for your library
DICTIONARY OF
ORGANOMETALLIC
COMPOUNDS
The recent growth in organometallic chemistry
has Jed to an explosion in the
number of organometallic compounds
discovered or synthesized.
How can scientists working in this
area locate reliable data on all
reaJJy important organometallic ?
The answer lies in the new Dictionary
of Organometallic Compounds,
published in November 1984.
• provides within 15,000 Entries an extensive • provides a continually up-to-date information
yet selective compilation of the most important system with Annual Supplements
organometallic compounds
• entries compiled by subject experts under
• for each compound, details of structure, supervision of a prestigious international
physical and chemical properties, reactions and advisory board
references are provided in clearly set out and
• a time-saving, cost-saving and reliable
easily scanned Entries
resource essential to all users of organometallic
• offers access to compounds by structure, compounds
molecular formula, chemical name, or CAS
Registry Number From a review by F.A. Cotton, Texas A & M
• the structure index contains reduced images University
of all the structure diagrams in the section - a 'This extraordinarily useful compendium is
unique feature which allows users to 'browse', one that no chemical enterprise having the
and to appreciate quickly the full range of types slightest involvement in organometallic
of compounds which have been synthesized chemistry would want to be (or would be
wise to be) without.'
Publication date: November 1984 ISBN: 0 412 247 10 0
286 x 213mm 3,000 pages in three volumes
For further information please write to The Promotion Department,
Chapman and Hall, 11 New Fetter Lane, London EC4P 4EE.
SPRINGER-SCIENCE+BUSINESS MEDIA, B.V.
Introduction
1. Using the Sourcebook (2) Any compound with an established use, such as
in catalysis, as a synthetic reagent or starting material.
The Sourcebook is divided into element sections:
(3) Other compounds of particular chemical,
within each section the arrangement of entries is in
structural, biological or historical interest, especially
order of molecular formula according to the Hill
those thought to exhibit unusual bonding characteris
convention (i.e. C, then H, then other elements in
tics.
alphabetical sequence of element symbol; where no
carbon is present, the elements including H are Some compounds which are not considered
ordered strictly alphabetically). sufficiently important to justify separate entries of
Every entry is numbered to assist ready location their own have been included as derivatives in the
and the entry number consists of a metal element entries of other compounds. These may include for
symbol followed by a five-digit number. example:
Indexes (1) Organic derivatives in the classical sense.
(2) Don&-acceptor complexes.
There are three printed indexes: a name index which
(3) The various salts of an anion or cation. In
lists every compound name or synonym in alpha
nearly every case, the entry for an ionic substance
betical order; a molecular formula index which lists
refers to the naked anion or cation, and the molecular
all molecular formulae, including those of deriva
formula, molecular weight and CAS registry number
tives, in Hill convention order; and a CAS registry
given for the main entry are those of the ion, in
number index listing all CAS numbers included in the
agreement with current CAS practice. Salts of the ion
Sourcebook in serial order. All indexes refer to the
with various counterions are then treated as
entry number. In the name index an entry number
derivatives and the molecular formulae of all of these
which follows immediately upon an index term means
are given.
that the term itself is used as the entry name but an
( 4) Oligomeric compounds. Where a compound is
entry number which is preceded by the word 'see'
known in several states of molecular aggregation
means that the term is a synonym to an entry name. In
these are all included in the one entry, which usually
all three indexes an entry number which is preceded
refers to the monomer. Compounds which are known
'by the word 'in' refers the reader to a specified
only in dimeric form are entered as such, but the
stereoisomer or derivative which is to be found
hypothetical monomers are included as derivatives to
embedded within the particular entry.
ensure that the names and molecular formulae of the
In addition to the three printed indexes, each
monomeric forms occur in the indexes.
element section (except where the section is very
short) is preceded by a graphical structure index All names and molecular formulae recorded for
allowing the rapid visual location of compounds of derivatives occur in the Name and Molecular
interest. The structure index reproduces all structure Formula Indexes respectively.
diagrams present in that element section in reduced
size and printed in entry number order.
The following paragraphs summarize important
3. Chemical Names and Synonyms
considerations in compiling the information in this
Sourcebook. For more detailed information, see the The naming of organometallic compounds is
Introduction to the Dictionary of Organometallic frequently problematic and so in selecting the range
Compounds from which this Sourcebook derives. of alternative names to present for each compound or
derivative, editorial policy has been to report names
2. Compound Selection which are found in the literature, including Chemical
Abstracts, and not to attempt to impose a system of
In compiling this Sourcebook the aim has been to
nomenclature. The editorial generation of new
include from the primary literature up to mid 1983:
names has therefore been kept to a minimum
(1) Compounds representative of all important required by consistency. Most names given in the
structural types (typically, the parent member of each Sourcebook are those given in the original paper(s)
series, where known, together with a selection of its and in Chemical Abstracts.
homologues). Names corresponding to those used by CAS during
ix
Introduction
the 8th, 9th, and lOth collective index periods for each element there are chapters on the use of
(1967-71, 1972-6 and 1977-81 respectively) are organometallics in organic synthesis and catalysis.
labelled with the suffixes SCI, 9CI and lOCI
Comprehensive Inorganic Chemistry, Trotman
respectively. Dickenson, A.F. eta!. Eds, Pergamon, Oxford, 1973.
Contains information about organometallics as well
as discussions of oxidation states, coordination
4. Toxicity and Hazard Information
chemistry and analysis of the metals.
Toxicity and hazard information is highlighted by the Gmelins Handbuch der Anorganischen Chemie,
sign[> which also appears in the indexes. 8th Edn, Springer-Verlag, Berlin. Some volumes of
Gmelin covering organometallic compounds have
All organometallic compounds should be treated as if
been updated relatively recently and can therefore be
they have dangerous properties.
consulted for comprehensive data on some types of
The information contaiiiM'ln the Sourcebook has organometallics. Some Gmelin element sections,
been compiled from 'so~rces believed to .be reliable. however, arc many years out of date.
No warranty, guarantee or representation is made by Houben-Weyls Methoden der Organischen Che
the Publisher as to the correctness or sufficiency of mie, 4th Edn, Band XIII, Metallorganische Verbin
any information herein, and the Publisher assumes no dungen, Thieme-Verlag, Stuttgart.
responsibility in connection therewith .. The Chemistry of the Carbon-Metal Bond, Hartley,
The specific information in this publication 'on the F.R. and Patai, S. Eds, Wiley, New York, 1982-.
hazardous and toxic properties of certain compounds Contains sections on the synthesis, analysis and
is intended to alert the reader to possible dangers thermochemistry of various classes of organometallic
associated with the use of those compounds. The compounds.
absence of such information should not, ho"wever, be Transition-Metal Complexes of Phosphorus,
taken as an indication of safety in use or misuse. Arsenic and Antimony Ligands. McAuliffe, C.A.
Ed., Macmillan, London, 1973.
Methods of Elemento-Organic Chemistry, Koches
5. Bibliographic References
hkov, K.A. Ed., North Holland, Amsterdam, 1967.
The selection of references is made with the aim of MTP International Review of Science: Inorganic
facilitating entry into the literature for the user who Chemistry, Series 2, Emeleus, H.J. Ed., Butter
wishes to locate more detailed information about a worths, London; University Park Press, Baltimore,
particular compound. Reference contents are fre 1974-5.
quently indicated using mnemonic suffixes. In Advances in Organometallic Chemistry, Academic
general recent references are preferred to older ones, Press, 1964-.
and the number of references quoted does not Annual Surveys of Organometallic Chemistry,
necessarily indicate the relative importance of a Elsevier, 1964-7.
compound. Organometallic Chemistry Reviews, Elsevier,
Journal abbreviations generally follow the practice 1966-7.
of Chemical Abstracts Service Source Index (CASSI). Organometallic Chemistry Reviews, Section A:
In patent references, no distinction is made between Subject Reviews 1968-72.
patent applications and granted patents. Organometallic Chemistry Reviews, Section B:
Annual Surveys 1968-74.
Journal of Organometallic Chemistry: This incor
6. Sources of Further Information
porates reviews and surveys after the discontinuation
The following books and review series provide more of the two series of Organometallic Chemistry
information about various aspects of organometallic Reviews.
chemistry. Lists of reviews specific to organic Organometallic Chemistry, 1972-, (Specialist
compounds of particular metals may be found in the Periodical Reports), RSC.
introductory sections of the metals concerned. Coordination Chemistry Reviews, Elsevier, 1966-.
Progress in Inorganic Chemistry, Interscience,
General
1959-.
Comprehensive Organometallic Chemistry, Wilkin Advances in Inorganic Chemistry and Radio
son, G. et al. Eds, Pergamon, Oxford, 1982. This chemistry, Academic Press, 1959-.
book represents the most complete and up to date
review of the whole subject. In addition to sections
X
