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Book Review Metal Complexes in Aqueous Solution. By A. E. Martell and R. D. Hancock. (Series Modern Inorganic Chemistry. Series editor J. P. Fackler Jr

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BOOKS
ters 7 and 8 review the latest developments
in the area of integrated optics and fiberoptic sensors.
The following three chapters are devoted to the basic concepts in the fields of
nanostructured materials (Ch. 9), nanotechnologies (Ch. 1 I), and molecular electronics (Ch. 10). Chapter 9 emphasizes
the innovative possibilities arising from
the latest developments in nanostructured
materials. However, the subject is treated
too briefly here, covering only a few aspects of the synthesis of the materials and
the production of thin films. There are no
examples of applications of such materials
in sensors. In Chapter 10 special attention
is given to the importance of understanding the molecular and atomic processes
for developing high-performance chemical sensors. Some prime examples are gas
sensors based on inorganic films in which
charge transfer occurs by a variety of
mechanisms, other types of gas sensors
depending on host -guest interactions,
and the principles of function and recognition in biosensors using enzymes, antibodies, and cellular membranes. There is
also a short description of the principles
of molecuIar electronics and bioelectronics, and the use of pattern-recognition algorithms in chemical sensor technology.
Chapter 11 presents a rather speculative
subject-nanosensors. According to the
definition given here for an nanosensor, it
must have one of the following properties
at nanoscale: sensitivity, surface area at
which the interaction occurs or characteristic dimensions. The examples described
are displacement sensors working in the
nanometer and picometer ranges, forcemeasuring sensors based on the STM
principle, optical near-field nanosensors,
and Hall effect nanosensors. Apart from
the optical sensors all these structures
are produced by micromachining of silicon.
The purpose of the second part of this
volume is to disseminate reliable information about the market for sensors. The
analysis of the market for innovative sensors and microsystems is arranged under
the following six key areas: aerospace industry (Ch. 13); industrial process control
(Ch. 14); medical and clinical applications
(Ch. 15); environment (Ch. 16); automobile industry (Ch. 17); production engineering and quality control (Ch. 18). The
authors of this report describe basic requirements for measurements, and technical and commercial limitations that are
specific to each of the fields discussed.
They also give information about the size
of the market and the commercial significance of already existing products, the requirements for new types of products in
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the area of sensors, and potential new
markets.
The book as a whole is set out in a clear
and systematic style, and has a comprehensive index. It can be recommended for
all scientists and technologists who are
looking for a systematic overview of the
current state of sensor and microsystem
technology, despite the risk that a book
dealing with such a rapidly developing
area of research may quickly become outdated. University and technical college
students of sensor and microsystem technologies should also have access to this
work, at least through a library.
Alexandre Choulga
Institut fur Chemo- und Biosensorik e. V.
Munster (Germany)
Metal Complexes in Aqueous Solution. By A . E. Martell and R . D . Hancock. (Series: Modern Inorganic
Chemistry. Series editor: J. P. Fucklev, J r . ) . Plenum, New York, 1996.
253 pp., hardcover $59.00.-ISBN 0306-45248-0
The two authors of this book have been
engaged in research in coordination
chemistry for many years and have contributed greatly to the subject. They have
done much detailed work on the determination of thermodynamic quantities for
metal complexes and the interpretation of
such data in relation to steric and electronic effects in metal-ligand interactions. These studies form the subject of
the book reviewed here.
An introduction, which includes a brief
historical survey and a concise summary
of the most important physicochemical
quantities relating to metal ions, is followed by three chapters in which the thermodynamic aspects of metal-ligand interactions are discussed in detail. Taking a
representative selection of monodentate
ligands as illustrative examples, the authors describe the essential characteristics
of complex formation, first in the gas
phase then in aqueous solution. The increased stabifity with multidentate ligands
(chelate effect) and with macrocycles
(macrocyclic effect) is explained by conformational considerations based on
molecular mechanics calculations. In particular, the authors show that some commonly accepted ideas, such as the explanation of the chelate effect purely in terms
of entropy, or the assumption that the selectivity of macrocyclic ligands can be predicted from the diameter of the molecular
cavity, are incorrect or at least oversimplified. The second part of the book presents
Verlagsgesellschaft mbH, 0-69451 Wemherm, 1996
some topical examples from biology and
medicine, such as chelate therapy, contrast agents for magnetic resonance imaging, and radiopharmaceutical applications. The authors give a survey of the
various ligands that are currently used,
and present some ideas for the design of
new tailored ligands. The book ends with
a short description of experimental methods for determining stability constants.
Each chapter contains a detailed list of
references to original publications, although with a definite emphasis on the
authors’ own work.
In view of the great importance of metal
complexes in present-day medicine, biology, and environmental chemistry, the appearance of an authoritative work on the
subject by two recognized experts is very
welcome. Nevertheless, the wide-embracing title of the book leads one to expect
more than the authors have included here.
For example, reversible electron transfer
processes play an important role in the
chemistry of transition metal complexes
(e.g., one need only think about the respiratory chain), and yet there is nothing at
all here on redox reactions (with regard,
for example, to the question of how the
ligand shell affects the redox potential).
Again, there is no discussion of hydrolytic
polymerisation. One very important reaction pattern exhibited by metal complexes
is the formation of polynuclear aggregates
with 0x0 or hydroxo bridging, and should
at least have been given a mention (for
example, in the summary of possible types
of reactions on pp. 221 -222). The kinetics of ligand substitution are touched on
only briefly in the introduction, and the
authors do not take the opportunity to go
into more detail later. One searches in
vain for important keywords such as
“frans effect” and “base catalysis”. The
discussion of experimental methods concentrates mainly on potentiometric techniques [including passages in Sections 7.4
to 7.7 that are mostly taken word-forword from the book Determination and
Use of Stability Constants, by A. E.
Martell and R. J. Motekaitis (VCH Verlagsgesellschaft, 1988)l. Other methods
such as NMR and ESR are mentioned
briefly but are not explained in more detail.
Most of the (inevitable) printing errors
are of a kind that do not interfere significantly with one’s understanding. However, there are some regrettable mistakes,
for example in the legend and labeling of
Figure 2.19. In Sections 5.5 to 5.9 there
are problems with the numbering system
used for the ligands, as the numbers in the
text do not agree with those in the graphics. Water ligands should be denoted by
0570-083319613520-2406 S 15 00-t 2510
A n w w ChPm Int Ed Fnol 1996 7 5 &I ZO
BOOKS
“aqua” rather than “aquo” according to
IUPAC recommendations. The text as a
whole could have been written somewhat
more concisely. The frequent repetitions
detract from the clarity of the book; for
example, Fables 5.1 and 6.4 are identical.
Equation 6.1. which reads:
logK,(multidentate) = log PJunidentate)
+ ( n - 1)log 55.5 corresponds to Equation
3.1, which is identical except that there
“multidentate” is replaced by “polydenlate”. Figures 3.16 and 6.10 show the
same linear plot of logK(DF0) against
log K ( O H - ) (relationship between the
free energies), except that different values
are given for Pu4’! On the other hand,
some of the explanations given in the introductory chapter (Ch. 1 ) are a little too
brief. For example, in Figure 1.S the various metal centers are classified into
“hard”, “soft”, and “borderline” types
(Pearson’s HSAB principle). Here Fe and
Cu are classed as “borderline”, Ag as
“soft”, and G a as “hard”, without any
indication of oxidation states. Although
these assignments are appropriate for Fe”,
Cu”, Ag‘, and Gar“, the same is not true
for Fell’. Cu’, Ag”, and Gal.
To sum up. this book can be recommended for advanced undergraduate students, as well as for researchers working
in the areas of coordination chemistry,
aquatic chemistry, medicinal chemistry,
and bioinorgdnic chemistry. It will give
them a better understanding of the selectivity of metal complexing agents and
provide valuable insights for the design of
new tailored chelate ligands. However,
the discussions are confined to thermodynamic aspects of mononuclear complexes
(treated from an unconventional and also
rather one-sided point of view). In this
respect the book does not fully live up to
its title.
Kaspar Hegetsch nviler
Institut fur Anorganische Chemie
der Universitat des Saarlandes
Saarbriicken (Germany)
Stereochemistry of Coordination
Compounds. By A . von Zelewsky. Wiley, Chichester, 1996. 254 pp., paperback & 24.95.4SBN 0-471-95599-X
This book on the stereochemistry of coordination compounds goes well beyond
the basic information typically found in
textbooks of inorganic chemistry, and
even covers recent developments in the
chemistry of complexes, such as helicates,
complexes of macropolycycles, and
siderophores. The emphasis is on “topographical stereochemistry”, an aspect that
deals with the type and number of stereoisomers and their symmetry properties.
The book is essentially concerned with
“classical” complexes, so that organometallic compounds and clusters are not
treated, for good reasons that are explained on page 9. The literature references provided (over 500) give the reader
access to the original papers to study topics in greater depth.
In the introduction (Ch. 1) the author
mentions the important contributions of
Alfred Werner, whose coordination theory, formulated towards the end of the 19th
century, was based mainly on stereochemical considerations. The clarity of this
chapter could have been improved by separating the many figures and inserts more
obviously from the running text, since the
reader might easily lose the thread of the
discussion in a few places.
Chapter 2 contains a critical discussion
of the experimental methods used for investigating the stereochemical structures
of coordination compounds. Chapter 3
then gives a brief survey of the most important types of coordination geometry
for complexes of main-group and transition metals. Unfortunately Table 3.1 (p.
31) contains several blunders: for example, the commonest coordination geometry for Cu“ is the square-pyramidal,
not the tetrahedral.
Chapter 4 deals with some basic concepts of topographical stereochemistry,
beginning with genera1 considerations regarding the symmetry and isomerism of
metal complexes, and continuing with a
classification of ligand types. In deciding
which stereochemical nomenclature to
use, the author opts for a sensible compromise. In general he follows the IUPAC
rules for the nomenclature of inorganic
compounds, but in the interests of clarity
he occasionally departs from these in
some details and adopts alternative principles. Thus, the introduction of several
different reference systems for describing
the chirality of metal complexes (pp. 6770) seems entirely appropriate. On the
other hand, it takes a little while to get
used to some of the unconventional symbols introduced on pages 40-46, such as
A = A for planar chelate ligands and
A = A for nonplanar ones.
Chapter 5 treats the stereochemistry of
mononuclear coordination compounds,
illustrated by many examples. Here, if not
earlier, the discussion of stereoisomeric
octahedral chelate complexes (pp. 119128) reveals one of the main strengths of
the book, in that the discussions are supported by a wealth of informative examples. Even complex macrocyclic and
macropolycyclic ligands and siderophore
complexes are included. Here, however, I
feel I must make a correction (p. 148): the
first flexible polyazamacrocycle was synthesized as early as 1937 by Alphen, well
before the work of Curtis in 1960. The
figures in all the chapters have been prepared with much care, and I noticed
scarcely any errors [although Fig. 5.73(i)
on p. 159 is incorrect].
In Chapter 6 the reader is introduced to
the more complex multinuclear systems,
beginning with compounds having simple
bridging hgands such as hydroxide,
halide, o r bipyrimidyl. In supramolecular
coordination compounds such as the helicates and Sauvage’s molecular chains and
loops, the stereochemistry is of central importance.
Finally, Chapter 7 deals with stereochemical processes in the reactions of coordination compounds. Due to the complexity of this subject, only selected
aspects could be covered. Here the main
emphasis is on isomerizations and substitutions at the metal atom. Other topics,
such as reactions of coordinated ligands
and enantioselective catalysis, are treated
only briefly.
To summarize, the book Stereockemistry of Coordinalion Compounds is an excellent and clearly set out reference source
for chemists working on metal complexes,
with a wealth of examples and many figures. The reader should be able to quickly
extract information on a wide range of
problems in static stereochemistry. Furthermore, the book is well written from a
teaching standpoint and should be suitable for use by advanced students, although the subject matter is quite specialized for these readers.
Roland Kramer
Anorganisch-chemisches Institut
der Universitat Miinster (Germany)
c
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