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Book Review Carbonylation. By H. M. Coloquhoun D. J. Thompson and M. V

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the localization of coke deposition (within the porous structure of the zeolite, or on the outer surfaces ofthe crystallites).
Chapter 13 (H. W. Kouwenhoven and B. de Kroes) is concerned with the preparation of zeolite catalysts. The main
emphasis is on the manufacture of catalysts for the fluidized
catalytic cracking (FCC) process, which is the most important method for producing gasoline constituents from
higher-boiling products. Many of the reactions used for the
conversion of hydrocarbons are acid-catalyzed, and in
Chapter 12 P. A. Jacobs and J. A. Martens give an introduction to acid-catalyzed reactions on zeolites. Especially useful
here is the section dealing with shape-selective catalysis on
acidic zeolites, which is one of the most important areas of
application of zeolite catalysts. In (shape-selective) catalytic
reactions and selective adsorption/separation processes, the
rate of diffusion is a key variable, and this is discussed in
Chapter 11 by M. F. M. Post. Chapter 10 by R. P. Townsend
is concerned with ion exchange in zeolites; the use of zeolite
NaA as an alternative to phosphate in detergents is based on
its ion exchange properties. In Chapter 9 R. A. van Santen,
D. P. de Bruyn, C. J. J. den Ouden, and B. Smit give an
introduction to the theory and modeling of zeolites; they
discuss theories of the lattice stability of zeolites and of adsorption and acidity, computer modeling of zeolites, and the
simulation of adsorption and diffusion. Chapters 7 and 8 are
concerned with methods for characterizing zeolites. In
Chapter 7 J. H. C. von Hoff and J. W. Roelefsen discuss
methods for determining structure and defects, pore size,
chemical composition, acidity, morphology, and particle
size. In Chapter 8 G. Engelhardt describes the application of
solid state NMR spectroscopy to studies of zeolites. He discusses the capabilities of *’Si and 27AlNMR spectroscopy
using the magic-angle-spinning (MAS) technique, and the
important question of determining the relative proportions
of framework and non-framework aluminum and of
“NMR-invisible” aluminum ions. MAS-NMR spectroscopy
with I7O, “B, ‘H, 13C, or 31Pas the observed species also
has potential applications to non-zeolitic molecular sieves.
Chapters 4 to 6 are concerned with the synthesis of molecular sieves. In Chapter 4 J. 0.Jansen and S. T. Wilson in turn
review the synthesis of zeolites and of molecular sieves, respectively, with AlPO, as the starting material. The details
concerning the synthesis of relatively large single cyrstals of
some of the zeolites will undoubtedly arouse much interest.
In Chapter 5 on “Modified Zeolites” R. Szostak describes
secondary and post-synthesis treatments, such as the various
methods for extracting aluminum from the zeolite framework. In Chapter 6 R. A. Schoonheydt discusses the transition from the two-dimensional clay minerals to the pillared
clays with three-dimensional structures, which exhibit
molecular sieve properties. In these the diameter of the channels is greater than in zeolites, and consequently the critical
molecular diameter up to which molecules can undergo conversion in the cavity system is greater.
At the beginning of the book the editors list the special
characteristics of zeolites: a uniform pore system, an interior
surface that is accessible to reacting molecules, exchangeability of the ions, and the possibility of tailoring the size of the
pore entrances and the acidity to suit particular applications.
In Chapter 1 these characteristics are discussed in lucid detail
by L. Moscou, thereby smoothing the way for newcomers to
the subject. In Chapter 2 E. M. Flanigen presents a historical
outline of the synthesis and use of zeolites. The structures of
zeolites are discussed in Chapter 3 by H. van Koningsveld.
Appendix I lists the structural characteristics of some of the
most important molecular sieves, and Appendix I1 contains
information on pore sizes and on structural isotypes. Both
662
0 VCH Verlagsgesellschaft mbH.
W-6940 Weinheim, 1992
these appendixes are especially useful for the beginner. The
detailed subject index enables one to quickly locate information on desired topics.
Each chapter begins with the fundamentals, then goes on
to describe the latest results, citing publications up to 1989.
The clear arrangement of the contents makes for easy readability. However, it would have been better to use the
Geneva nomenclature throughout for the subject headings.
This is a very useful book for beginners as well as specialists,
and it can be recommended for everyone with an interest in
this field.
Michael Nimz
Institut fur Anorganische und Analytische Chemie
der Technischen Universitat Berlin (FRG)
Carbonylation. By H. M . Colquhoun, D. .
I
Thompson and
M. V. Twigg. Plenum Press, New York/London, 1991. XI,
296 pp., hardcover $65.00.-ISBN 0-306-43747-3.
This book is devoted to transition metal based carbonylation chemistry leading to the synthesis of carbonyl compounds. Following discussion of concepts and practical aspects, it is organized according to the type of organic
compound being synthesized (e.g., aldehydes, amides). The
last chapter deals with recipes for catalyst preparation and
recovery.
The brief introduction provides a good perspective of carbonylation chemistry, past and present. Why this book is
timely is well-reasoned in this chapter.
The second chapter is entitled “Reaction Mechanisms in
Carbonylation Chemistry”. What an excellent contribution,
especially for organic chemists! This chapter deals with the
nature of metalLC0 bonding, elementary steps in catalytic
processes (e.g., oxidative addition), and new mechanistic
patterns in carbonylation reactions. The explanation of
catalysis is first-class, and the critical analysis which the
authors provide here and throughout the text is refreshing.
There are a few weak points; for example, while electrophilic
attack on carbon monoxide is adequately explained, a more
in-depth treatment of nucleophilic attack at carbonyl carbon
would have been useful. Nevertheless, this logically organized examination of mechanism and synthesis in carbon
monoxide chemistry is the best in the literature.
The third chapter is concerned with the handling of carbon monoxide in the laboratory, and the techniques used in
the experiments. This is essential for anyone Contemplating
research in carbonylation reactions.
The following seven chapters include critical accounts of
the synthesis of aldehydes, ketones, carboxylic acids, esters,
amides (including anhydrides, aryl halides, urethanes, ureas,
and isocyanates), lactones, and lactams. The organizational
aspects are excellent, and the authors also highlight areas
where further research is desirable. The treatment of the
subject in each case is very good, and occasionally includes
natural product syntheses. Nevertheless, more details could
have been provided in some cases. For instance, the mechanism of the Stille reaction is interesting and merited coverage
on pedagogic grounds. Also, no reference is made in the
book to the interesting work of Sue Thomas and co-workers
on the conversion of a,P-unsaturated ketone complexes to
ketenes with carbon monoxide. An inconsistency is the notation of the oxidation state of the metal, which is designated
in equations, schemes, etc. in some chapters, but not in others.
0570-0833/92/050.7-06623 3.50+.25/0
Angew. Chem. Int. Ed. Engl. 31 (1992) N o . 5
A chapter is devoted to a thoughtful analysis of decarbonylation reactions, the reverse of carbonylation processes.
This transformation is useful in certain situations, and clearly more work is required in this area.
The final chapter provides experimental procedures for
the synthesis of many of the catalysts described in the book.
This is a useful contribution, as is the description of methodology for the recovery of metals.
In conclusion, this impressive book is well-written, enjoyable to read, and will be of genuine value to chemists.
Cathleen Crudden, Howard Alper
University of Ottawa
Ottawa (Canada)
Chemometrics. Applications of Mathematics and Statistics to
Laboratory Systems. By R. G . Brereton. Ellis Horwood,
Chichester, 1990. 307 pp., hardcover $76.50.--ISBN 0-13131 350-9
The purpose of this monograph, which is published as an
independent volume in the “Ellis Honvood Series in Chemical Computation, Statistics and Information”, is to familiarize the experimental chemist with the capabilities and advantages of chemometric methods.
The book proceeds mainly by using simple examples to
briefly explain the principle of each of the chemometric
methods described, then illustrating how they can be applied
to real chemical and analytical problems. This approach has
the advantage that the emphasis is on understanding the
mathematical and statistical methods used. In describing
computer-based methods the author frequently gives details
of the wide choice of software that is commercially available,
and is in most cases adequate for the purpose. A brief account of the development of chemometrics is followed by an
introductory survey of up-to-date literature on chemometrics. The following six chapters describe, in a clearly organized division of subject matter, the most important chemometric methods and their applications.
The chapter on experimental design describes the use of
sequential methods such as simplex optimization, factorial
plans, multilinear regression methods and variance analysis
for the quantitative modeling and optimization of chemical
experiments. Next the author describes both well-established
methods (control card techniques, the cusum method, autocorrelation analysis) and newer methods (the autoregressive
moving average method, the variogram, the Kriging method
and the Nyquist frequency) that are used as aids in investigating time series in chemistry and for dealing with the complicated problem of representative sampling. Chapter 4 describes the many different methods for selecting and
optimizing the conditions for analyses, such as principal
component analysis, information theory, classification procedures, simplex methods, and Fourier and Hadamard
transformations. The next two chapters are concerned with
the application of univariate and multivariate methods in
signal processing. Here there is some overlapping with topics
in the previous chapter (e.g. Fourier transformation and
principal component analysis), which is an unavoidable consequence of the wide range of uses of chemometric methods.
Techniques described under the heading of univariate signal
processing include moving average calculations, deconvolution of signals and Kalman filtering. The discussion of factor
analysis as a tool for multivariate signal processing omits to
give details of the estimation of communalities; however,
Angew. Chem. I n r . Ed. Engl. 31 (1992) No. 5
6
there is a brief description of the modern method of target
transformation factor analysis. In the section on multivariate calibration some important regression methods using latent variables, such as principal component regression and
PLS regression, are mentioned but only described very
briefly.
The final chapter, which deals with pattern recognition,
includes comprehensive descriptions of unsupervised learning methods, especially algorithms for cluster analysis, and
the supervised learning methods using either “hard” (linear
discrimination analysis, linear learning machine, K nearest
neighbors) and “soft” (SIMCA) techniques, as well as
“fuzzy” methods.
The user will need to supplement the reading of the short
appendix on important mathematical operations by also
studying appropriate monographs on mathematical statistics. The appendix does not deal with the use of “robust”
statistical methods.
The typography is relatively free of errors, apart from a
few exceptions (e.g. Equation 3.5 and Table 5.20), and is very
clear. This monograph, with its clear layout of subject matter
and the easily understood and well chosen examples of applications in chemistry and analysis, offers a good basic
grounding for the experimental chemist who wishes to become involved in chemometrics; also readers who already
use mathematical and statistical methods in their area of
work will find here new ideas for applying chemometric
methods.
Jiirgen Einax
Institut fur Anorganische und Analytische Chemie
der Universitat Jena (FRG)
Bonding and Structure: Structural Principles in Inorganic and
Organic Chemistry. (Series: Inorganic Chemistry. Series
editor: J; Burgess.) By N . u! Alcock. Ellis Horwood,
Chichester, 1990. 321 pp., hardcover $ 50.95.--ISBN 013-465253-3
The introductory remarks in a book on chemical bonding
and structure can provide a very good indication of its underlying philosophy; here, in a chapter entitled “The Evidence”, the author clearly states his position: all that we
require to know are the positions of the atoms in space and
the resulting total energy. In the first forty pages the reader
is given a good brief survey of the experimental methods
whereby structural information can be obtained (X-ray diffraction, NMR, IR, electron diffraction, neutron diffraction,
etc.) and of the sorts of structural phenomena that can appear. Already one becomes aware of two things: 1) crystal
structures dominate the discussion from the start, and
2) quantum chemistry, which has now developed into a very
reliable method for determining molecular structures and
one that can no longer be overlooked, is here ignored. Moreover, the author fails to keep to the promise made in the title,
as the book is mainly concerned with inorganic solids.
In a 100-page chapter entitled “Ideal Bonds” the properties
of metallic, ionic and covalent bonds are described. The description of the underlying quantum mechanical principles is
extremely brief and lacks clarity. The LCAO concept is dismissed in a few lines. In discussing the stationary state wavefunctions of hydrogen the real and complex representations
are mixed up. The 1s wave function is given in Equation (l),
i,h(r) = 2a0 - 6.5 exp(- riao)
VCH Verlagsgesellschaft mbH, W-6940 Weinheim. 1992
0570-0833/92/0505-0663 $3.50+ .ZSjO
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663
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