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Book Review Orbital Interactions in Chemistry. By T. A. Albright J. K. Burdett and M. H

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(e.g. the boron containing boromycin), and for the macrotetrolides, which complex alkali metal ions specifically. In
contrast, avermectins and milbemycins are dealt with in a
chapter of their own (by M . H. Fisher and H. Mrozik), no
doubt on account of their promising antiparasitic properties.
This book will be a useful aid, above all to natural products chemists, biochemists and microbiologists. It may also
have much to offer medical personnel with an interest in
chemistry.
Walter KeNer-Schierlein [NB 713 IE]
Laboratorium fur Organische Chemie
der ETH Zurich (Switzerland)
Vom Wiirfelspiel zum Naturgesetz. Simulation und Modelldenken in der Physikalischen Chemie. By G . Marsch.
VCH Verlagsgesellschaft, Weinheim 1985. x, 269 pp.,
bound, DM 58.00.--ISBN 3-527-26226-1
There has been no lack of attempts to present the difficult material of physical chemistry in a simple and didactically skillful manner in the past. The author has nevertheless been successful in finding a new approach which is
particularly addressed to the mathematically less experienced reader. He presents a selection of dice and board
games in order to illustrate some of the fundamental concepts of statistical thermodynamics and reaction kinetics.
Individual chapters deal with game models for the Maxwell distribution of velocities, the Boltzmann distribution,
the concept of entropy, and various aspects of chemical
reactions. The final chapter includes games for the illustration of several problems from different fields including the
theory of chromatography, light absorption, crystallization, and phase separation of liquids.
The compilation under consideration is a success, reflecting the author’s long experience in university instruction. Little more than a knowledge of the most elementary
mathematical concepts and operations is assumed. The
reader learns more difficult concepts, such as that of entropy, “as a player.” Historical details of the development of
statistical thermodynamics enrich the book decidedly. In
the chapter on chemical reaction kinetics, the author also
includes quite recent examples taken from oscillating reactions and processes of molecular selection. In this chapter,
the algorism developed by Gillespie of the simulation of
chemical processes would have fit in well, above all since it
is well suited to illustrate the extrapolation from the extremely small numbers of statistical events in the games to
the laws of kinetics in real systems. The section covering
games played on a pocket calculator will surely be very
useful to the reader. It is unfortunate that the author has
not included microcomputers too, which are accessible almost everywhere nowadays, and on which many aspects of
university instruction can be quickly demonstrated in a didactically effective manner.
On the whole, this excellent monograph is an enrichment of the literature used in physical-chemistry instruction. It can be warmly recommended to students and university teachers alike. Senior physicists and chemists will
also discover much of interest in this work: old, familiar
material appears in a new light when looked at through
“game-glasses.”
Peter Schuster [NB 736 IE]
Institut fur Theoretische Chemie und Strahlenchemie
der Universitat, Vienna (Austria)
Angew. Chem. In!. Ed. Engl. 25 (1986) No. 6
Orbital Interactions in Chemistry. By T. A . Albrighr. J . K .
Burdett, and M . H . Whangbo. Wiley, Chichester 1985.
xv, 447 pp., bound, L 63.25.--ISBN 0-471-87393-4
As preface, let me say that in spite of the large number
of books on the market dealing with the principles, methods, and applications of M O models in various fields of
chemistry, the book under consideration could f i l l a gap
that has been recognized not only by those who are engaged in teaching this area of theoretical chemistry, but
also and especially by all those-whether advanced students or research colleagues-who want to learn MO theory as a “tool”.
The content and presentation of this book are obviously
strongly influenced by the theoretical approach and by the
didactic example of the scientific mentor of the three authors, Roald Hoffmann, whose Preface to the book is well
worth reading. Within the realm of the possible, this work
comes very close to satisfying its very high aim: the transmission of a qualitative, sound understanding of the electronic structure, geometry, and reactivity of compounds,
ranging from simple molecules to solids. This understanding is based on a model that is as universally useful as possible, the model of interacting orbitals. The consequent utilization of the fragment-orbital formalism runs like a red
thread through the entire book. According to this formalism, the orbitals of complex molecules are built up from
simple orbital building blocks, or fragments, using a few,
straightforward interaction rules from perturbation theory.
In the beginning chapters, the theoretical foundations
and formalisms are discussed in the necessary depth. Only
little mathematical knowledge is required, a consideration
that is not totally unimportant for a book’s wide acceptance by chemists. The treatment is neither tiring nor unnecessarily extensive, considering the aims of the book. Here,
chapters are found covering AO’s and MO’s, as well as the
qualitative rules for orbital interactions and for the construction of correlation diagrams based on perturbation
theory; group theory, orbital symmetry, and an introduction to the fragment-orbital approach are also included. In
this section, hybridization, perturbations based on electronegativity and geometry, Walsh diagrams, and Jahn-Teller
distortions are treated. In an extraordinarily thorough and
detailed manner, and by means of many examples, the
qualitative derivation of the “appearance” of molecular
orbitals and of their relative energies is presented and
made clear to the reader using qualitative, pictorial representations. Thus, he learns to “think in orbitals”, progressing from simple, two-atom systems to complex molecules
and finally to solids. The chapter on the electronic structure of solids is especially attractive: the correspondence
between the MO picture of molecular entities, on the one
hand. and the band structures of crystalline solids, on the
other, as well as quasi analogous concepts and phenomena, are elaborated very well didactically. A bridge between molecular chemistry and solid-state physics can thus
be recognized. A clearly written chapter, immediately accessible even to non-theorists, dealing with the limitations
of the one-electron model in molecules, with electron-electron interactions, state energies, etc., including CI-wave
functions, has not been overlooked. This is important,
since most of the book is deliberately kept at the simple
one-electron valence-MO level.
Whereas the basic theory and applications presented in
the first half of the book are illustrated using organic molecules and light atoms as examples, it is predominantly
the series of chapters on the application of MO theory to
58 1
inorganic and organometallic transition-metal compounds, following a chapter on so-called hypervalent species and their MO theory, that make the book worth reading. A survey like the one that the three authors give here
has until now been lacking in the textbook field. A very
thorough treatment, not only of the basic types of organometallic fragments, ML,, and their bonding capability,
but also of questions concerning the electronic structure,
molecular geometry, structural dynamics, and reactivity of
metal complexes, is provided using numerous qualitative
M O and interaction diagrams. Hoffmann’s Isolobal Analogy, treated at the end of this part of the book, serves to
overlap and link inorganic with organic chemistry. This
concept has recently received wide application as a structural and even as a synthetic guideline, especially in the
organometallic field. It would have perhaps been useful if
the authors had pointed out a little more clearly that transition-metal fragments and complexes with the same orbital characteristics may nevertheless differ in their chemistry, depending on the position of the respective metal atom
within its group, on the actual charge, and on the appearance of special problems (relativistic effects, spin-orbit
coupling, etc.) with the heavier transition metals. A chapter
on cluster compounds closes the book.
The authors have chosen the subject matter and examples, especially in the section on transition metals, in such
a way that the book can be considered a review at the textbook level of the research performed in this field by Hoff
mann and his co-workers over the past ten years. Didactically, the book is a masterful achievement, and in this respect, the graphic work (formulas, MO diagrams, etc.) is in
no way inferior to the text. Misprints, inevitable in a first
edition, are not worth going into here. The references are
sufficiently numerous and suitably chosen considering the
aim of the book.
This book could be of great benefit to teachers and students alike. It could contribute to the understanding of
modern chemistry as an integrated whole, rather than as a
rigidly compartmentalized system. Much would be gained
if university teachers gave this book the same attention as
has been given to the original publications on which it is
based. It is unfortunate that the book’s price can only be
regarded as a n unreasonable demand and that students as
a rule will be prevented from purchasing it. As is so often
the case, a moderately priced, paperback edition would
have been more appropriate and more conducive to the
wider circulation and use of the book.
Peter Hofmann [NB 720 IE]
Anorganisch-chemisches Institut
der Technischen Universitst Miinchen (FRG)
RpqtTtered n a n i e ~ .rrodemorkr.
err med
08
Common Fragrance and Flavor Materials. By K . Bauer and
D.Garbe. VCH Verlagsgesellschaft, Weinheim 1985, 213
pages, hardback, DM 112.00.-ISBN 3-257-26038-2
In seven chapters of a monograph of 213 pages, the two
authors try to give an overview of the chemistry of flavors
and fragrances. The authors are predestined to d o so by
their profession, but succeed only partly. The classification
of odorous compounds according to their structure is of
course a possibility, but certainly not the clearest. This
leads to curious situations. Macrocyclic odorants can thus
be found in three different places, e.g. civetone on p. 56,
15-pentadecanolide on p. 104, and ambrettolide on p. 137.
A classification by odors would have shown the reader the
molecular similarities and structural variety that can cause
a typical type of odor. Also elsewhere such present knowledge of the relationship between structure and odor is not
covered. The relevant remarks in chapter 1 “Introduction”
are totally insufficient. The information about the sources
and the detailed descriptions of the odors of compounds
that are listed in the voluminous chapter 2 “Single Fragrance and Flavor Compounds” are an agreeable surprise,
but to give the boiling points, refractive indexes, and densities would have been justified 30 years ago, not today.
This is aggravated by the fact that modern analytical data
such as IR, N M R and MS are not given. As an extreme,
chapter 3 “Essential Oils”, lists the above “classical” physical constants of oils of different provenience in tabular
form. Pages 152 and 171 could have been omitted together
with another ten pages. Instead one would have wished
modern analytical data and also information about important oils not treated at all. If physical data are to be compared, why not GC-fingerprints?
Specialists will miss the trade names for quite a number
of odorants. 1,1,2,3,3,8-hexamethyl-6-oxa-2,3,5,6,7,8-hexahydro-lH-benzo[f] (p. 102) will be meaningless whereas
the name Galaxolide@will recall the odorous power of an
extraordinary musk substance. Lyral@(p. 58), Hedione@(p.
62) and LiliaP (p. 71) are some further examples. Even
names that can be found in most textbooks like Exaltolidea are not given. Exaltone@and a number of other modern odorants are not treated at all. Flavor compounds have
been specially neglected. The extraordinary richness of flavor compounds found, for example in the area of N - and
S-heterocycles has been compressed into two pages. Literature references are cited in a very liberal manner. Half of
them come from works called I S 0 and EOA, which will
mean nothing to chemists, who, according to the introduction, are included in the potential readership. The layout
and legibility are excellent, as is also the translation into
English.
Giinther Ohloff [NB 715 IE]
rhrr journal. e w n wifhour spewfic rndrrarion rhereol are nor
Firmenich AG, Geneva (Switzerland)
10 be
consrdered unprotecred h, lo“
0 V C H VerlagsgeselIsch;iit mbH. D-6940 Weinheim. 1986 - Printed ~n the Federal Republic of Germany by Zechnersche Buchdruckerel. SpeyerIRhein
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582
Angew. Chem. Int. Ed. Engl. 25 (1986) No. 6
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