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Blackwell Science, Inc.: Malden, MA, 1998. 285 pp. ISBN 0-632-04162-5. $54.95.
Informative, readable, unpretentious. That is how
I would describe Nicholas Long's book if I were asked to do
it in just three words. Indeed, the book under review is
a straightforward, balanced survey of metallocene chemistry
all across the periodic table, written in a textbook format
and aimed at advanced undergraduate and graduate students
and researchers in the field.
Covering from synthetic methodologies and
reactivity patterns to structural and bonding aspects of the
so-called "sandwich" complexes, it is a candid compendium of a
virtually limitless area of organometallic chemistry. It
is interesting to note that a more authoritative, two-volume set on
metallocenes was published almost simultaneously
(Metallocenes; Togni, A.; Halterman, R. L., Eds.; Wiley-VCH: New
York, 1998; ISBN 3-527-29539-9; $265.00). However, with
the exception of the title and year of publication, the latter
is quite different in scope and organization, having a
clear emphasis on early transition-metal chemistry and
separate chapters written by invited experts.
Long's book is divided into six chapters, starting
with Chapter 1 introducing the history and classification
of metallocenes. The author clearly states his desire to
present an overview of compounds containing only two or
more cyclopentadienyl (Cp) ligands, including parallel, bent,
main group, and multidecker species. Thus, almost
completely excluded from the text are monocyclopentadienyl
(half-sandwich) complexes and derivatives with heterocyclic
or conjugated ring systems. While this choice is
understandable in terms of space, perhaps even justifiable, I regret to find
only a marginal treatment of compounds with substituted
Cp ligands. It would have been useful, at least for those new
to the field, to summarize the distinctive features of bulky
Cp ligands, of which the pentamethylcyclopentadienyl (Cp*)
is probably the most popular. Furthermore, the application
of sterically demanding Cp ligands is one of the most
important synthetic strategies that have contributed to the
progress of organometallic chemistry in the last couple of decades or so.
Chapter 2 reviews the synthesis and physical
properties of metallocenes, including derivatives of the alkaline
earth, transition, and main group metals, the lanthanides, and
the actinides. The conspicuous absence in this chapter of a
section on metallocenes of the alkali metals is unfortunate
given the fascinating structural chemistry they exhibit, as seen
recently for the lithocene (LiCp2{), sodocene
(NaCp2{), and
triple-decker
Cs2Cp3{ anions (Harder, 1994, 1996),
whose structures are only hinted at in section 5.1.8 later in the
text. Chapter 3 deals with the electronic structure and bonding
in metallocenes and includes a lucid discussion of ionicity
vs covalency in Cp complexes. Chapter 4 outlines the
reactivity and spectroscopic properties of metallocenes, from the
extensive organic chemistry of ferrocene to the study of
fluxional processes in sandwich compounds. Chapter 5
contains a fairly detailed description of the synthesis, properties,
spectroscopy, and structures of bridged metallocenes
(i.e., metallocenophanes), followed by shorter sections on
polynuclear and multidecker derivatives. The last chapter is
perhaps the most interesting, and the author does an
excellent job presenting the main uses of metallocenes, from
olefin polymerization reactions to the design of new
ferromagnetic and nonlinear optical materials. It is also entertaining to
learn about some of the applications of metallocenes in
medicine, molecular recognition, asymmetric catalysis, and organic
synthesis. Each chapter is supplemented with some 20 to 40
selected references, some as recent as 199-97.
The book has been carefully produced and the
number of typographical errors (e.g., retardents instead of
retardants [p 269]) or inconsistencies (e.g., carbon and its heavier
congeners are referred to as group 4 elements in Chapter 3
[p 104] but as belonging to group 14 elsewhere in the text)
is minimal. Factual mistakes are even harder to spot, but
the structures of the tris(cyclopentadienyl) complexes
Cp3Sb and Cp3Bi are known (Lorberth, 1981, 1995), contrary to
what is alluded in Chapter 2 (p 76). Notwithstanding
these oversights, the book, on balance, is an attractive
overview of metallocene chemistry and I gladly recommend it.
In addition, I will prefer to buy Long's book and let the
library purchase Togni and Halterman's related treatise, whose
list price is almost five times higher. Whether the reader is
a beginner interested in learning basic organometallic
chemistry or a professional looking for a handy reference guide on
the subject, Long's text should appease anyone with an
appetite for sandwich compounds.
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