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Book Review Chemistry of Organosulfur Compounds. General Problems. (Ellis Horwood Series in Organic Chemistry). Edited by L. I. Belen'kii

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The number of printing errors is kept to a minimum
throughout this volume of Houben-Weyl. Less than 50 errors (and only very few serious ones) were noted while going
through the material. Except for p. XXXVII (where a terrible 20 % of the references contain minor errors or are incomplete) the citation is comparable in quality with that found in
the best journals.
In conclusion, the updated Houben-Weyl volume on
organotellurium compounds is a masterpiece which will be
enthusiastically received by all readers with an interest in
tellurium chemistry.
Lars Engman
Department of Organic Chemistry
Royal Institute of Technology
Stockholm (Sweden)
ElectrochemicalInterfaces. Modern Techniques for in-situ Interface Characterization. Edited by H . D . Abruna. VCH
Publishers, New York/VCH Verlagsgesellschaft, Weinheim, 1991. xviii, 589 pp., hardcover DM 182.00.ISBN 0-89573-715-913-527-27840-0
In seeking to describe and understand electrochemical
processes that occur in the solid/liquid transition region,
experimental data obtained by in-situ measurements are especially valuable. A classic example where this applies is the
technique of cyclovoltammetry (CV). In this the flow of
charge is recorded as a function of the potential, but the
method is intrinsically incapable of yielding information of
a highly specific kind. For this reason other techniques that
can be used in combination with CV have recently been
developed to complement it. Particularly interesting results
can be obtained by carrying out in-situ measurements simultaneously with CV studies. This rapidly developing field is
the subject of the specialist book edited by H. D. Abruna
(Cornell University) which is reviewed here.
The book, with nearly 600 pages, contains ten chapters
following an introduction by the editor, and there is a 22page subject index at the end.
The individual chapters deal with X-ray absorption spectroscopy, surface X-ray scattering, X-ray standing waves,
measurements of surface forces, surface-enhanced Raman
scattering, nonlinear optical methods, surface infrared spectroscopy, in-situ Mossbauer spectroscopy, radioactive labeling, and measurements with vibrating quartz crystals. The
contributions have been printed by the camera-ready
method, and all except one are written by American authors.
Apart from the fact that several of the figures in Chapter 1
have been interchanged (see the comments of the editorial
office), the contributions are impressively well prepared :
they are logically set out, illustrated by clear figures, and
packed with information. In each chapter the main emphasis
is firmly on the description of the experimental techniques,
but this is supported by informative examples of applications. In the description of the standing wave X-ray technique for characterizing the phase boundary region, it would
have been desirable to have examples of a wider range of
applications. Unfortunately the chapter on in-situ measurements with vibrating quartz crystals includes only two examples of applications, namely to coverages deposited in the
under-potential range, and (in more detail) to studies of mass
transport during redox processes in polymer films.
The selection of topics covered by the chapters is not exhaustive, nor can one expect it to be. However, it is notice238
0 VCH Verlagsgeselischafi mbH. W-6940 Weinheim, 1992
able that some important methods are not mentioned, for
example UVjVIS reflectance spectroscopy, ellipsometry and
photocurrent spectroscopy. It is also regrettable that in-situ
topographic methods such as scanning tunneling microscopy (STM) and atomic force microscopy (AFM),
which give a microscopic image of the surface, in some cases
with atomic resolution, are not included. Furthermore, there
seems to be no logical connection between the individual
chapters. The fact that articles on optically based techniques
alternate with others on non-optical methods prevents a systematic presentation of the subject matter. Consequently it is
hardly surprising that the book lacks a final summary linking the various methods and results and evaluating them.
The book has a binding of appropriately high quality.
Considered as a whole it provides a good insight into the
progress that has been made in the development of various
in-situ techniques. However, one cannot overlook the shortcomings in the choice of topics and their relative emphasis,
and the lack of a logical arrangement of subject matter, with
the result that the reader fails to get a deeper understanding
of the progress made. The book is unquestionably of considerable importance to scientists with interests in interfacial
electrochemistry, and it should therefore be in every relevant
library, especially since the price of DM 182.00 will prevent
students from buying it.
Rolf Schumacher
Schering AG, Forschungsabteilung GT
Berlin (FRG)
Chemistry of Organosulfur Compounds. General Problems.
(Ellis Horwood Series in Organic Chemistry). Edited by
L. I. Belen’kii. Ellis Horwood, New York, 1990. 378 pp.,
hardcover $ 129.95.-ISBN 0-13-132051-3
Organosulfur chemistry traditionally occupies a position
of considerable importance in Soviet research, and there is
even a special scientific committee to promote it. The monograph reviewed here is based on a status report on work in
this field that was prepared in 1986 by various authors,
mainly from Moscow and Irkutsk. For this English version
the Russian text has been rearranged and updated (but, as
becomes apparent, only in parts). The 15 chapters of this
version deal with the preparation of organosulfur compounds, their transformations, and the methods used to
study them. Details of the chapters are as follows: Modern
Principles of the Synthesis of Organosulfur Compounds
(M. G. Voronkov et al., 14 pp., 25 references); Radical Reactions of Some Thiocarbonyl Derivatives in Solutions
(R. Kh. Freidlina et al., 21 pp., 64 references); Thermal Reactions and High Temperature Syntheses of Organosulfur
Compounds (M. G. Voronkov et al., 20 pp., 56 references);
Photochemical Synthesis and Transformations of Organosulfur Compounds (N. N. Vlasova, 22 pp., 65 references);
Radiochemical Synthesis and Transformations of Organosulfur Compounds (E. M. Nanobashvili, 8 pp., 11 references); Sulfur-stabilized Carbanions and their Synthetic Use
(F. M. Stoyanovich, 43 pp., 267 references); Formation of
C-C Bonds Using Sulfur-containing Electrophilic Reagents
(W A. Smit et al., 32 pp., 99 references); Catalytic Synthesis
of Organosulfur Compounds (A. V. Mashkina, 20 pp., 40
references); Methods of Desulfurization and their Use in
Organic Synthesis (L. I. Belen’kii, 36 pp., 189 references);
Investigation of Organic Reactions by the Use of Radioactive Sulfur (V. M. Fedeseev, 15 pp., 49 references); Mass
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Angew. Chem. Int. Ed. Engl. 31 (1992) No. 2
Spectrometry of Organosulfur Compounds (A. A. Polyakova, 11 pp., 10 references); Electronic and Vibrational Spectroscopy of Organosulfur Compounds (Yu. L. Frolov,
11 pp., 30 references); 33SNMR Spectroscopy (V. M. Bzhezovsky et al., 21 pp., 49 references); X-Ray Fluorescence
Spectroscopy of Sulfur Compounds (G. N. Dolenko, 76 pp.,
199 references); Quantum Chemical Calculations of
Organosulfur Compounds (Yu. L. Frolov, 11 pp., 66 references).
The intention of the book is to concentrate on reporting
the work of Soviet authors, and the high proportion of references to Soviet publications makes this clearly apparent. In
contrast, published work in this field from the West is incompletely represented. Consequently, although the breadth and
potency of organosulfur chemistry become clearly evident,
some of the newer and particularly elegant synthetic applications of sulfur-containing functions, such as those introduced by Vedejs and by Warren, are dismissed too briefly or
even omitted altogether. Also the usefuless of the book is
reduced by the inadequacy of the rather meager subject index. For example, there is no entry for thioaldehydes, despite
the fact that this class of compounds is mentioned at several
places in the text. It therefore comes as welcome news to
learn from the preface that a further monograph dealing
with the most important classes of organosulfur compounds
is planned.
The book is visually pleasing, thanks to the clear and
attractive typography. The incidence of printing errors is as
low as can reasonably be expected. There is an unfortunate
mistake on page 84, where thiofenchone is shown instead of
thiocamphor. The book fills a gap by reporting in detail on
Soviet work in organosulfur chemistry, but for newcomers
to this field it fails to provide a comprehensive critical
overview.
Ernst Schaumann
Institut fur Organische Chemie
der Technischen Universitat Clausthal (FRG)
Chemical Kinetics. By K. A . Connors. VCH Publishers, Cambridge, New York/VCH Verlagsgesellschaft, Weinheim,
1990. xiii, 480 pp., hardcover DM 168.00.-ISBN 15608 1-006-8/3-527-28037-5
Spectacular successes were achieved during the sixties using the techniques of “fast kinetics”, and this led to the
publication of numerous monographs dealing with this important area of physical chemistry. As an example of these
one may mention particularly the classic work “Fast
Reactions in Solution” by E. F. Caldin. Since then these
methods have become widely used in chemistry, and therefore the publication now of an up-to-date and comprehensive work on kinetics, which will make it easier for those
interested in the topic to become involved, is greatly to be
welcomed.
This book by K. A. Connors deals in eight chapters with
the important field of kinetics in solutions, with an emphasis
on the chemical aspects. Chapter 1 begins with a discussion
of the significance of time as a variable in chemistry, followed by an explanation of fundamental concepts involved
in kinetics, such as transition states, reaction intermediates
and the rate of a reaction. The second chapter then deals
with the integration of simple rate equations, the determination of the order of a reaction, and the calculation of the
corresponding rate constants. The numerical problems assoAnxew. Chem. Int. Ed. Engl. 31 (1992) N o . 2
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ciated with error limits are discussed in great detail at this
stage. Chapter 3 deals with systems described by more complex equations, and here the application of Laplace transforms is introduced. Classical examples such as microreversibility and the condition for a stationary state are discussed, as well as more innovative methods such as MonteCarlo simulations.
Following these discussions of basic principles, Chapter 4
is concerned specifically with fast kinetics. After dealing with
diffusion-controlled reactions, the chapter goes on to consider periodic and aperiodic relaxation processes. Next some
fundamental aspects of nuclear magnetic resonance spectroscopy as applied to kinetic studies are discussed. The
chapter ends with descriptions of flow techniques, fluorescence quenching, and a brief reference to electrochemical
methods.
Chapter 5 takes the discussion of fundamental kinetic theories a stage further. Starting from the Arrhenius equation,
the author deals with simple collision theory, potential energy surfaces, and quantum-mechanical aspects of the reaction
between H, and H and of the transition state based on
partition functions. Next some examples from actual kinetic
studies are described, and the relationship between free activation enthalpies and free reaction enthalpies is discussed.
Here the Hammond, Brernsted, and Marcus representations
are discussed. Chapter 6 describes examples of some important kinetic phenomena. In the catalytic field the influence of
acids and bases on chemical reactions and the pH-dependence of rate constants are discussed. The chapter concludes
with a discussion of isotope effects, which are very interesting from a mechanistic standpoint.
For organic chemists the most interesting part of the book
is likely to be Chapter 7 on structure-reactivity relationships. The chapter begins with a discussion of linear free
energy relationships, by which activation data are related to
reaction parameters. As an example, these considerations
are applied to substituent effects in arenes, including a detailed discussion of the Hammett equation and its limitations. Next the theory is extended to nonlinear phenomena,
including electronegativity, polarizability and resonance effects. Substituent effects in aliphatic compounds are also
treated and discussed in relation to the Taft constants for
alkaline and acidic hydrolysis reactions; here steric effects
are also taken into consideration. In addition the “hardsoft” concept and isokinetic relationships are discussed. It is
pleasing to find that the potentially troublesome problem of
propagation of errors in determining activation parameters
is taken into account here, so as to avoid the risk that numerical errors could lead to wrong conclusions about isokinetic
relationships.
The book ends with a chapter on the influence of the
medium. It is shown that, in the determination of rate constants, differences as great as a factor of 10l5compared with
the gas phase can arise. Theories of the effects of a dielectric
continuum are discussed, including the early suggestions by
Born and also the Hughes-Ingold theory. The effects of intermolecular interactions with solvents are discussed, including molar refraction, polarization, Coulomb potentials,
charge transfer effects and hydrogen bonding. In this connection the empirical solvent scales based on thermodynamic
and spectroscopic data, such as those proposed by Gutmann, Kosower, or Reichardt, are especially important.
The range of topics covered in this book extends considerably beyond the treatments of kinetics found in comprehensive textbooks of physical chemistry. The numerous examples give an excellent overview of the many different types of
phenomena and reactions that have been studied. For the
Verlagsgesellschaft mbH, W-6940 Weinheim, 1992
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