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Book Review Sonochemistry The Uses of Ultrasound in Chemistry. Edited by T. J. Mason

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becoming generally appreciated once again, especially
through the rise of bioinorganic chemistry as a new field of
research. However, even leaving aside the remarkable catalytic capabilities of the metal centers in enzymes, many organic chemical transformations that are made possible or are
catalyzed by non-organometallic coordination compounds
are indispensable in laboratory synthesis and technological
processes. Whether one already has an interest in the subject
or has previously regarded classical coordination chemistry
as boring, weighed down with theory, and irrelevant, it will
be found that Constable’s account is a thoroughly readable
one that offers an agreeable way of catching up on developments. The main emphasis in this monograph is on using
(transition) metal centers to influence the reactivities of
organic compounds that have coordination sites formed by
heteroatom donors.
The particular features that make this an easy book to
read are its emphasis on synthetically useful reactions and
the absence of lists of physico-chemical data and literature
citations in the main text. References for further reading are
collected at the end of the book under topic headingswhere the author gives more detailed information.
Constable begins with a very brief introduction to the orbital models needed. Regrettably, however, the qualitative
description of chemical reactivity does not include catalytic
aspects. Coordinative bonding, both with and without x
interaction, is described from the standpoint of electrostatic
interactions and geometry in a clearly understandable way.
The descriptions of examples begin with the chapters on
attack by nucleophiles, including H,O and OHe, on metalcoordinated carbonyl compounds and their derivatives (nitriles, imines), on sulfur compounds, and on phosphoric acid
esters. These are followed by a chapter discussing electrophilic attack on metal-stabilized anions such as enolates
or thiolates and on neutral bases (e.g. metal-induced amineimine transformations).
Another chapter describes template reactions that lead to
ring closure, with a general discussion of the special characteristics of macrocyclic systems with regard to stability, resistance to attack, metal selectivity, and geometric strains
caused by imperfectly matching metal ions. Supramolecular
structures, including knotted molecules, continue to be a
source of fascination. The special characteristics of aromatic
substrates are discussed, with particular emphasis on the
substitution reactions of metal-coordinated N-heterocycles
of the pyridine type. The description of redox processes is
limited to transition metal catalyzed reactions with 0, ,
which are of practical importance, but whose mechanisms
are not always as they seem at first sight. It is pleasing to note
that here, at last, a clear distinction has been made between
the processes of electron transfer, dehydrogenation, and
oxygen transfer. The final chapter, entitled “Envoi”, contains a very brief, and consequently rather simplified
account of the search for an overall rationalization of
the catalytic capabilities of coordinated metal ions in enzymes.
The contents of the book are clearly arranged and well
presented, matching the author’s excellent lecturing style.
The many formulas are well prepared, except for a few ring
systems and the inconsistent use of arrows for coordinative
bonds. The popular structure diagrams as reproduced from
X-ray diffraction studies are few in number so that the reader
obtains a rather limited appreciation of the complex geometries. On the other hand, the summaries given at the end of
each chapter and the pithy critical evaluations scattered
throughout the text are especially useful. Thus, for the reader
who, for a relatively small cost in time and money, wishes to
Angew. Chem. Int. Ed. Engl. 30 (1991) No. 10
acquire as much practical, useful knowledge of coordination
chemistry as possible, this book is recommended unreservedly.
Wo[fgang Kaim [NB 1131 IE]
Institut fur Anorganische Chemie
der Universitat Stuttgart (FRG)
Sonochemistry: The Uses of Ultrasound in Chemistry. Edited
by I: J. Mason. The Royal Society of Chemistry, London
1990. 151 pp., paperback $89.25.-ISBN 0-85186-293-4
Chemical applications of ultrasonic waves, often referred
to as sonochemistry, enjoyed a renaissance in the eighties.
These books are introductory in nature, intended for the
chemist with a potential interest in the field. The first is more
general, while the second will be of more interest to synthetic
chemists.
There are nine contributors covering an important range
of topics in eleven chapters: I:J. Mason provides an
overview of the field in the first chapter (8 pages, 10 references) dealing with historical aspects, non-chemical uses of
ultrasound (diagnostics), power ultrasound, and specific examples of ultrasound enhanced chemical reactions. The incorrect attribution of Regen’s work on dichlorocarbene to
Repic is unfortunate. Chapter 2 (“Sonochemistry, the General Principles”, .L P . Lorimer, 18 pages, 5 references) offers
a lucid discussion of wave propagation, particle displacement due to a longitudinal wave, factors affecting cavitation,
and the fate of a bubble in a sound field. It is one of the best
chapters in the book, marred only by the conspicuous absence of a discussion of the “hot spot” theory and Suslick’s
vapor shell.
The third chapter (“Ultrasound in Diagnosis, Inspection,
and Monitoring”, C . S. Gartside and M . M . Robins,
20 pages, 6 references) is simply out of place and dilutes the
effort of such a small book. Chapter4, (“Power Ultrasound”, J. P . Perkins, 13 pages, 5 references) deals with
some important fundamental concepts such as monitoring
acoustic input and output, construction of the transducer,
cavitation phenomena, health and safety aspects, and large
scale applications, but would be more effective if blended
efficiently with topics in Chapters 2 (see above), 5 (“A Survey of Commercially Available Sources of Ultrasound Suitable for Sonochemistry”, I:.L Mason, 9pages, no references), 10 (“The Uses of Ultrasound in Chemical
Technology”, I: J. Mason, 6 pages, 13 references), and 11
(“Scale-up Considerations”, I: J. Goodwin, 14 pages,
4 references). There is a good deal that is useful in these
chapters but the fragmentation of information and unnecessary repetition detract from them.
Chapters 6 (“Ultrasound in Organic Synthesis”, R. S.
Davidson, 17 pages, 38 references), 7 (“Free Radical Reactions under Sonochemical Conditions”, J.-L. Luche,
15 pages, no references) and 8 (“Ultrasound in Heterogeneous Catalysis”, J. Lindley, 8 pages, 89 references) discuss
much of the important literature of interest to synthetic
chemists. It is distracting that a number of the references in
Chapters 6 and 8 are simply incorrect and others have an
author’s name misspelled.
There is overlap among the chapters that a small book can
ill afford. As examples, precious space is wasted on two
discussions with schemes by Davidson and Luche, of Luche’s
free radical ring closure of benzamide and of his elegant
preparation of dialkylzinc compounds. Likewise, Davidson’s
treatment of continuous ultrasonic hydrogenation of soy-
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bean oil and platinum catalyzed hydrosilation belong only in
Lindley’s chapter where they are also discussed. Chapter 9
(“Ultrasound in Polymer Chemistry”, J. P. Lorimer,
20 pages, 10 references) covers theory of high frequency
waves (> 1 MHz) as well as applications in providing information on relaxation phenomena. Uses of low frequency
waves (polymerization/depolymerization)are also given.
Ultrasound in Synthesis. By S. K Ley and C. M . Low.
Springer, Berlin 1989. 133 pp., hardcover, $79.50.ISBN 0-387-51023.
Following a very brief introductory chapter (1 page),
Chapter 2 (“The Physical Basis of Sonochemistry”,
27 pages) provides a qualitative discussion of the origin of
and the factors influencing sonochemical reactivity. The current thinking on the cavitation process and the roles of frequency, intensity, temperature, and cell and probe design are
presented, along with a discussion of methods of measuring
ultrasonic intensity. This chapter will be useful to the novice
in the field.
The remainder of the book summarizes applications of
ultrasonic waves to synthesis, and covers organic, inorganic
and organometallic examples. The chapter titles and page
count illustrate the organization of the book. The treatment
is broad with only the highlights in each area covered: Chapter 3 (“Aqueous Sonochemistry”, 4 pages); Chapter 4 (“Preparation of Activated Magnesium”, 6 pages); Chapter 5
(“Preparation of Organoaluminum Compounds”, 1 page);
Chapter 6 (“Application of Ultrasound to the Preparation
of Organolithiums”, 1 I pages); Chapter 7 (“Reactions with
Other Alkali Metals”, 11 pages); Chapter 8 (“Organozinc
Reagents”, 16 pages); Chapter 9 (“Intercalation Reactions”, 1 page); Chapter 10 (“The Effects of Ultrasound on
Enzyme-Catalyzed Reactions”, I t pages); Chapter 1 1 (“UItrasonic Acceleration of Organic Reactions”, 19 pages);
Chapter 12 (“Ultrasonic Acceleration of Redox Reactions”,
6 pages); Chapter 13 (“The Effects of Ultrasound on Transition Metal Catalysts”, 2 pages); Chapter 14 (“Transition
Metal Carbonyls and Ultrasound”, 15 pages).
Chapters 11 and 12 emphasize homogeneous phase-transfer and nonmetal reactions, although there is some overlap
with metal-based reactions. Perhaps a different organization
of material would have avoided this and the need for the oneand two-page chapters (5, 9, 10 and 13). Considering the
hefty price tag, a more judicious dse of space is required for
good value. For example, the diagrams and schemes are too
large for a book this size, as are the spaces allotted for chapter headings, leading to far too much white space. The aim
of this book is to familiarize a wider audience with the background of chemical applications of ultrasound. This is accomplished at the “acquaintance” level.
Philip Boudjouk [NB 1139 IE]
Department of Chemistry, North Dakota State University
Fargo, ND (USA)
Corrigendum
In the communication “On a Metathesis Reaction of
Tetrathiafulvalene (TTF)” by Henning Hopf et al. (Angew.
Chem. Int. Ed. Engl. 30 (1991) 1127), the first sentence in the
discussion of the crystal structure of compound 4 a should
read as follows: Its structure in the crystal is characterized by
an almost orthogonal arrangement of the phenyl ring and of
the heterocycle containing S1 and S2 with respect to the
largely planar rest of the molecule (dihedral angle between
the best planes, 96 and 79”, respectively). In reference [9] the
lattice constant b is 1443.3(3) pm.
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Angew. Chem. In!. Ed. Engl. 30 (1991) No. 10
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