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Book Review Dynamic NMR Spectroscopy. By J. Sandstrm

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BOOK R E V I E W S
Carbanion Chemistry. By R. B. Bates and C . A . Ogle.
Springer-Verlag, Berlin 1983. vii, 117 pp., bound, DM
48.00.
The title and size of this work raise hopes of an introduction to carbanion chemistry; there is an unfilled need
here, since the most recent introduction is already ten
years old.
However, the foreword reveals that the authors’ aspirations are much lower: “This book was prepared with the
idea of collecting together some of the multitudinous new
literature on carbanions and presenting it along with the
fundamentals of carbanion chemistry”. Furthermore, an
emphasis is promised on results published in the years
1976-1982 with about half of the 785 references.
Eight chapters (74 pp.) deal with the structure, synthesis
and reactions of carbanions and organoalkali metal, alkaline earth, aluminium, zinc and cadmium compounds in an
exceedingly compressed form. Chapter IX (2 pp.) “Carbanion Equivalents” might well have been omitted without
incurring any loss of relevant information; the compilation
of (very arbitrarily) chosen synthetic equivalents for not directly accessible carbanions, without commentary, is
scarcely helpful. The alternative-a detailed inclusion of
preparative applications-would fall outside the framework of this little book.
The number of topics covered in such a small space
means that problems can only be touched upon and deeper
insights cannot be conveyed. Attempts to extract principles
are only occasionally made and even then seem mostly superficial. Thus, concerning the regioselectivity of electrophilic substitution of dianions (a field in which Bates is involved) we are only presented with the following rule of
thumb (p. 42): “. .. the first reaction with an electrophile
will occur where the last proton came off (assuming the
dianion was generated by removal of protons)”. Apart
from the fact that there are many exceptions to the rule
(amongst other reasons because several CH acids can act
as precursors for the same dianion), the reader is given no
aid in further understanding.
Recent developments, such as dominate the carbanion
literature today and which were already in full progress in
1981 (e.g. the stereoselective substitution of carbanions,
the change of selectivity by metal exchange, and lithiations
directed by heteroatoms), can be recognized by the insider
but they merge in the uniformity of the material.
Did the authors just wish to offer assistance in the rapid
tracing of original publications? If so there are some minus
points to be awarded here. First, they do not fulfill completely the promise they give in the foreword, since only
five publications are cited from 1982 (of which three are
the authors’ own). Furthermore, the reviewer was not able
to discover what the criteria were for selecting the literature. Which of the publications are the most important is
usually controversial. Apart from this, the literature from
German-speaking areas seems to be greatly underrepresented. Only a few groups from this sector may find their
contributions adequately represented. The number of references (from a total of 785) is a rough and ready but telling measure: Seebach (21), Schlosser (6), SchiiZlkopf ( 5 ) ,
Kauffmann (4), Hiinig (2), Bestrnann (l), R. R . Schmidt (I),
Reetz (l), etc. Basic publications also remain unmentioned. For example, there is no mention of the extremely
useful allopolarization principle (Gompper, review 1976) or
of Boche’s publications concerning the torsion dynamics of
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ally1 anions; the list could be extended. It is also troublesome that reviews are not labeled and that there is no author index.
The numbers of mistakes and printing errors have been
held down to acceptable levels. In spite of the inadequacies discussed this book can be recommended to all who
are concerned with carbanions, because everyone will find
topics of interest to him amongst the abundance. The newcomer, however, is recommended for introduction, the exciting reading of “Schlosser” (published by the same company in 1973)-Struktur und Reaktivitat polarer Organometalle-as a preliminary.
Dieter Hoppe [NB 641 IE]
Institut fur Organische Chemie
der Universitat Gottingen
Dynamic NMR Spectroscopy. By J . Sandstrom. Academic
Press, London 1982. x, 226 pp., bound, $ 39.50.
This book is neither a new edition nor a substitute for
the standard work of the same name published by Jackman
and Cotton in 1975. Those expecting a survey of the most
important new DNMR investigations will be disappointed.
To be sure almost all the techniques (with the exception of
2 D experiments) are mentioned and typical areas of application presented using examples (ligand permutations of
transition metal complexes are missing); however the book
is not intended to be a literature compendium but an introduction, stimulation and reference work for the planning
and execution of one’s own experiments.
Three chapters cover the theoretical basis : the modified
Bloch equations for exchange, the application of density
matrix formalism to coupled spin systems, the theory of T,
and TI and saturation transfer experiments. The density
matrix chapter assumes knowledge of the quantum mechanical description of NM R spectra and linear algebra. A
large proportion of interested chemists will probably omit
these sections and utilize the currently available computer
programs on a “black box” basis.
The following three chapters introduce the practice of
spectrum recording and analysis. Thus, sample production,
choice of solvent, temperature measurement, line shape
evaluation using approximation formulas or total line
shape simulation and statistical and systematic errors in
activation parameters are among the subjects that are
given a detailed and competent treatment. This central section of the book together with the next two chapters. covering specialized techniques (the application of lanthanoid
shift reagents, 13C-DNMR, DNMR in the gas phase, etc.)
and worked out examples, constitute the most impressive
part of the book. A great deal of information scattered
throughout individual publications, is summarized here.
Even readers already experienced in DNMR spectroscopy
will come across some useful information.
The latter part of the book is an introduction to computational methods for the determination of activation barriers. Alongside a short synopsis of quantum mechanical
calculations, force field calculations are presented for
pseudorotation in ring systems and for rotation in triarylmethyl compounds.
“Sandstrom” is a book that should be on everyone’s
desk who is a starter in dynamic NMR spectroscopy. Had
Angew. Chem. Int. Ed. Engl. 23 (1984) No. I1
such a book been available in the infancy of DNMR spectroscopy then a large proportion of the false enthalpies
and entropies of activation that have given DNMR spectroscopy its reputation for inaccuracy would never have
been published.
Martin Feigel [NB 618 IE]
Institut fur Organische Chemie
der Universitat Erlangen-Nurnberg (FRG)
Membranbiochemie. By H. Sandermann. Springer-Verlag,
Berlin 1983. v, 131 pp., bound, DM 44.00.
Membrane biochemistry sounds attractive.-The author
promises an introduction at the molecular level to biological processes in and at membranes, with emphasis on the
properties of the proteins, the lipids, and the polysaccharides bound to them. The book is intended as a university
text for students who have completed a basic course in biochemistry and wish to know more about the molecular aspects of membranes, a topic that usually receives only a
short treatment in biochemistry textbooks. The requirement is there; one is full of wonderment as to how the
topic will be treated in 125 pages.
Many key words of membrane investigation are
sketched out in ten chapters: types of membranes, membrane isolation, structure and properties of lipids and biological membranes, methodological approaches to the
study of membranes, detergents, membrane proteins including their biosynthesis and isolation, lipid protein interactions, transport through membranes, regulation of the
activity of membrane-bound enzymes, chemiosmosis and
ATP production, the importance of the polysaccharides on
the cell surface including the biosynthesis of glycoproteins
and as far as the metabolism of environmental chemicals.
In view of the size of this little book the abundant and
highly interesting range of topics damps expectations from
the start: it can only consist of a synopsis, which provides
the student with key words and hints for further readingwhich is no bad thing in itself.
Here, however, one of the failings of the book becomes
evident: there is a dearth of references. Methodological
approaches to membrane and protein isolation are
sketched using several examples. The labeling of a method
with a name or a classification as a pioneering piece of
work is of little use to the reader. Experimental data, thermodynamic quantities and their interpretation originating
from a topical and continually changing area of investigation must be made capable of being placed chronologically
and subjected to verification by quoting their sources. This
is of particular importance when, as on p. 64, models and
analysis are contradictory or various models are compared.
Alone the sources of figures are quoted in the figure legends. The general reference to two review journals at the
end of the book is valueless without further specification.
Standard biochemistry textbooks cannot be recommended
forfurther reading, since this little book is intended to supplement them.
The book is derived from a course of lectures and is in
its first edition. Because of this there are mistakes; however, they pass the bounds of the acceptable: printing errors,
forgotten or wrong units, unacceptable abbreviations and
units, errors in chemical formulas and incorrect labeling of
axes characterize the book and bewilder the student.
In addition to this there are, particularly in the physicochemical observations, imprecisions of language and conAnaew. Chem. Int. Ed. E n d . 23 (1984) No. I 1
fusing argumentations. Unexplained and uncheckable values, as for example on p. 109 concerning the statistics of
hexose combinations, should be avoided. Displaced and
irregular print in almost all the mathematical formulas
make reading more difficult.
What a pity-a good idea, a good beginning, very well
chosen material. The strength of this book lies in the descriptive biochemical-biological aspects. The molecular
principles, reproduced through physical-biochemical considerations, leave much to be desired, and there is a lack of
clear presentation. Perhaps this little book is a beginning;
it is certainly not a matured textbook and at a price of 44
DM cannot be recommended to university students, at
least in its present form.
H.-J. GUNU [NB 639 IE]
Institut fur Organische Chemie
und Biochemie der Technischen
Hochschule Darmstadt (FRG)
Elementary Statistical Thermodynamics. A Problems Approach. By N . 0. Smith. Plenum Press, New York 1982.
xiv, 216 pp., bound, $ 25.00.
Much of the evidence concerning the properties of molecules and their behavior depends on the application of
statistical thermodynamics. It should therefore occupy a
relevant place in the education of chemists. One of the reasons why this is not universally true may well be that access to this field is not particularly easy: Firstly it is not immediately obvious to the student how the chances of a
gambler in a numbers game are related to the specific heat
of an alcohol or the lifetime of an activated complex. It is
not surprising that American authors in particular attempt
to provide students with as smooth an entry as possible
into statistical thermodynamics. This little book is an example of a compromised attempt: Some knowledge of
chemical thermodynamics, simple functions, differentiation and integration, the treatment of series and some combinatorial analysis is assumed. Even the reminder that
O! = 1 has not been forgotten. The author employs IUPAC
nomenclature and SI units.
The individual chapters of the book cover the usual topics: The statistical mechanics of distinguishable particles ;
the statistical basis of entropy; thermodynamic functions
for systems of localized and distinguishable particles (with
the Einstein and the Debye crystal models); systems of
non-localized and indistinguishable particles; the thermodynamic functions of ideal gases: Here there is a careful
explanation of translational, rotational, vibrational and
electronic partition functions, the contribution of the
atomic nucleus, ortho- and parahydrogen, and of the influence of internal rotation. This is followed by the statistical thermodynamic calculation of chemical equilibria.
Each chapter is accompanied by cleverly chosen exercises, which not only improve understanding of the basic
material but also communicate a feeling for the magnitudes of the relevant thermodynamic probabilities, partition functions, entropies, etc. Some of the exercises are
worked through in the text, the solutions to the others are
included in an appendix.
The book seems to incorporate a great deal of teaching
experience. It can be recommended as an introduction to
students of chemistry and other sciences who have sufficient knowledge of English-it is also suitable as a “teach
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