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Book Review Phase Transfer Catalysis. Selected Problems and Applications. By Y. Goldberg

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BOOKS
A Broad Base from Theory to Applications
Cluster Ions. (Wiley Series in Ion
Chemistry and Physics.) Edited by
C-I: N g , 7: Baer and I. Powis. Wiley,
Chichester, 1993. 479 pp.. hardcover
E 80.00-ISBN
0-471-93830-0
This book contains a survey of recent
developments in fundamental research on
cluster ions. It consists of seven chapters, mostly concerned with van der
Waals clusters, although carbon and
silicon clusters are
also included. The
title is in fact too
broad. suggesting
to the reader that
metal clusters are
also covered.
First W. Kamke describes cluster studies using the photoelectron-photoion coincidence (PEPICO) technique, dealing
both with the experimental aspects and
with applications to van det- Waals systems. This method is very effective for
recording photoelectron spectra of sizeselected neutral clusters, especially when
applied with electrons of zero kinetic energy (threshold photoelectrons, TPE). The
use of the technique is illustrated by examples. such as studies of the unimolecular decay of noble gas clusters, charge
transfer in mixed clusters, and ionmolecule reactions in ammonia clusters.
The next chapter by C. Lifshitz is concerned with the unimolecular and collision-induced decomposition of protonbound clusters and carbon cluster ions.
F o r the first of these ion types, with the
general formula H '(MJ, excitation typically results in a solvent molecule M being
This Section contains book reviews and a list of
new books received by the editor. Book reviews are
written by invitation from the editor. Suggestions
for hooks to be reviewed and for book reviewers
are welcome. Publishers should send brochures or
(better) books to Dr. Ralf Bauniann, Redaktion
Angewandte Chemie, Postfach 10 11 61. D-69451
Weinheim. Federal Republic ofGermany. The editor reserves the right of selecting which books will
be reviewed. Uninvited books not chosen for
review will not be returned.
A n g i w . Clwm. Inr. Ed, EngI. 1994, 33, No. 15/16
"evaporated" off within a few microseconds. By measuring the kinetic energies of
the ejected molecules one can determine
bond energies, and collision-induced dissociation reveals isomeric structures. The
section on carbon clusters deals particularly with the currently fashionable fullerenes C&, C&, and C& and their novel
chemistry. In Chapter 3 M. F. Jarrold describes the many unique features of the
physics and chemistry of positive and negative silicon cluster ions. The author has
worked intensively in this field, using a
variety of experimental methods to obtain
the fullest possible information. Some of
his results from drift-tube measurements
are in striking disagreement with those
obtained by Smalley's group using
Fourier transform ion cyclotron resonance; the reason for this discrepancy is
not yet known.
The fourth chapter by J. M. Lisy describes vibrational spectroscopic studies
of solvated proton and metal ion clusters
which serve as models for dilute electrolyte solutions. An interesting result is
that proton clusters generated in a corona
discharge are relatively cold, and consequently more than one infrared photon is
needed for dissociation, whereas the metal
ion clusters, which are produced by association and are relatively warm, are dissociated by only one CO, laser photon. Next
(Ch. 5) J. M. Farrar reports on the electronic photodissociation of mass-selected
van der Waals clusters. mainly with regard
to the influence of solvation on this process. The closer one approaches to the
condensed phase, i.e. the greater the number of solvent molecules attached to the
central ion, the further the absorption is
shifted towards the infrared. Measurements of this effect are reported for several systems; for example,'the addition of up
to six ammonia molecules to Sr' shifts the
absorption maximum from about 400 nm
to about 1400 nm. However, the number
of ligands is still insufficient to simulate
the transition from gas phase clusters to
the liquid phase. Noble gas clusters are
the subject of Chapter 6, by I. Last and
T. F. George, then in the final chapter
B. G . Brunetti and F. Vecchiocattivi report on autoionization dynamics of collision complexes. In a typical experiment
VCH Verlugsgrsrllrcliafi mbH, 0-69451 Weinhrim, 1994
noble gas atoms are excited into
metastable states by electron impact, then
atoms of a single metastable species are
selected by optical excitation and are allowed to collide with a reaction partner
under thermal conditions. Whereas the
average time needed for a collision is
about
s, autoionization takes place
in about
s. After describing the experimental technique the authors discuss
applications involving hydrogen. mercury, alkali metal, and noble gas atoms,
and molecules such as N,, CO. CI,, H,O,
and even CF,CI.
The individual chapters are carefully
written, and the authors are acknowledged experts in the areas covered. I greatly enjoyed reading the book and can
recommend it unreservedly to other physical chemists in the field.
Munfrcd P.Irion
lnstitut fur Physikalische Chemie
der Technischen Hochschule
Darmstadt (FRG)
Phase Transfer Catalysis. 3rd Revised
and Enlarged Edition. By E. IY
Dehmlow and S. S. Dehmlow. VCH
Verlagsgesellschaft, Weinheim/VCH
Publishers, New York, 1993. 499 pp.,
h a r d c o v e r DM 188.00, $ 125.00--ISBN 3-527-28408-7/1-56081-206-0
Phase Transfer Catalysis. Selected
Problems and Applications. By Y
Goldbevg. Gordon and Breach,
L o n g h o r n e , PA, 1993. 456 p p . , hardcover $ 170.00 ($95.00 if ordered
from t h e publishers by private individuals).-ISBN
2-88124-870-5
Phase transfer catalysis (PTC) has
nowadays become an indispensable tool
for organic synthesis. Many reactions can
be carried out more efficiently and selectively by this method, and others for
which it has been used were not even possible previously.
The above book by Dehmlow and
Dehmlow replaces the second edition
published ten years ago, having been updated and, where necessary. revised. It includes many new developments in PTC.
057(1-0833.'94:1515-166Y 3 iO.OO+ .75/0
1669
The literature coverage now extends to
mid-1990, while at the same time some
outdated references have been dropped.
There are 1700 new literature citations,
bringing the total to over 3600. now listed
(unlike the earlier editions) in alphabetical
order. The subject index too is a valuable
aid when working with this book.
Goldberg‘s book on the same subject is
based on one originally published in Russian in 1989. which has been revised and
updated for this English version. It contains about 1300 literature references extending up to 1991. The subject index.
which is mainly substance-orientated, is a
useful working aid.
The book by Dehmlow and Dehmlow
begins with two chapters of more than
60 pages altogether on the theoretical
basis of PTC. The first chapter is mainly
concerned with the principles underlying
the effectiveness of the most important
types of catalysts, while the second deals
with the mechanistic aspects of the different variants of the PTC method. Chapter 3 (over 300 pages long) is concerned
with synthetic applications of PTC. It begins with a section on the choice of reaction conditions, such as the type and
quantity of catalyst, the solvent, and the
stirring rate. Particular attention is given
to enantioselective PTC, describing its applications, problems. and the many potential sources of error. Next the authors describe various practical applications of
PTC, arranged so far as possible according to reaction types. These include substitutions leading to alkyl halides, nitriles,
esters, thiols. sulfides. and ethers. N - and
C-alkylations, alkylations and acylations
of ambidentate anions, isomerizations,
H / D exchange reactions. and additions at
C = O and C = N bonds. Also treated in
detail are r-, p-, and y-elimination reactions, the preparation of phosphonium
and sulfonium ylides. nucleophilic aromatic substitutions, applications of PTC
to organometallic compounds. and reducrims and oxidations. I t is pleasing to find
that as well as giving well-proven synthetic recipes the authors include general principles that have been derived for carrying
out various types of transformations under phase transfer conditions. The large
amount of factual information is very
clearly presented. often in the form of
tables. enabling the reader not only to
quickly find specific details but also to get
an overview of a chosen area.
Goldberg’s book differs considerably
from that of Dehmlow and Dehmlow.
both in emphasis and in structure. A first
chapter (24 pp.) dealing with the theoretical fundamentals is followed by several
chapters describing some selected areas of
application of PTC. Chapter 2. the
longest in the book with about 100 pages.
is concerned with PTC in the chemistry of
N-heterocycles. Alkylations and acylations of compounds of this class are described, as also arc reactions of halogenated N-heterocycles with nucleophiles.
Reactions of N-heterocycles with carbenes are treated next, followed by oxidations and reductions, as well as the use of
PTC in the preparation of such compounds. In Chapter 3 (about 50 pp.). on
PTC in organometallic chemistry, much
attention is devoted to reactions iiivolving
organosjlicon compounds; other reactions discussed include those of mercury.
molybdenum, tungsten, iron, cobalt, and
platinum compounds. Chapter 4 (about
70 pp.) is devoted to catalysis by metal
complexes under phase transfer conditions, including reductions, oxidations.
dehydrogenations, and carbonylations.
Chapter 5. on three-phase catalytic reactions (about 30 pp.), discusses the advantages and disadvantages of using quaternary onium salts. crown ethers. or
open-chain polyethers immobilized on
polymers or other substrates for a variety
of reactions. In Chapter 6. on asyminetric
phase transfer catalysis (about 50 pp.),
Goldberg discusses in great detail a number of types of reactions for which PTC
has proved more or less successful. He also analyzes a number of experiments that
failed completely and were thus of no interest for synthetic purposes, and identifies the factors that previously led to
wrong interpretations. These latter discussions are extremely valuable for any
chemist intending to apply PTC to asymmetric syntheses for the first time. However. reactions giving optical purities of
15-19% should not be regarded as satisfactory, as is implied on page 299. Chapter 7 (about 40 pp.) is concerned with less
common variants of PTC; here the author
discusses cationic reactions, reactions at
phase boundaries between neutral species.
inverse PTC, electron phase transfer, and
reactions under the influence of ultrasonic
excitation at phase boundaries.
The book by Dehmlow and Dehmlow
is a standard work on PTC. affording the
reader a comprehensive overview ranging
from the theoretical fundamentals to the
diverse wealth of practical applications of
this useful method in synthetic chemistry.
It is an indispensable monograph for every chemist. being suitable not only for
organic chemists with experience of PTC
but also for those about to use this
method of synthesis for the first time.
Goldberg’s book does not give such a
comprehensive picture. nor was that the
author’s aim. Instead it is intended for
specialists. Because of this quite different
approach it may be regarded as complementary to the Dehmlow and Dehmlow
monograph. extending the subject and
treating it in greater depth, with detailed
discussions of many applications of PTC.
At some points one might say that it gives
too much information-for example, the
details given beside the reaction arrows of
the synthesis schemes. In both books the
subject matter is clearly arranged, in a
readable style, and in a sturdy binding.
No library should be without them.
Fritz Theil
Institut fur Angewandte Chemie
Berlin-Adlershof (FRG)
Fundamentals of Nuclear Magnetic
Resonance. By J. W Hennel and J.
Klinowski. Longman, Harlow (UK),
1993. 288 pp., paperback f 22.50.ISBN 0-582-06703-0
In their preface the authors formulate
their aim: it is to explain the physical and
mathematical basis of NMR sinTp/y but
exactly. In a certain sense they succeed.
However, the question is: what m e the
fundamentals of nuclear magnetic resonance? In the opinion of the authors they
are the magnetic dipole moment (of a
compass needle, a current loop. an orbiting electron, or a nucleus with a spin), the
magnetization of a macroscopic sample in
thermodynamic equilibrium. the Larmor
precession of an isolated spin, Bloch’s
equations, the Fourier transformation,
the Zeeman and dipolar parts of the
Hamiltonian. the method of (second)
moments, and the spin-echo and COSY
experiments.
Sure, all these topics are fundamentals
of NMR. and I would regard it as almost
a moral obligation of all those who practise N M R to be thoroughly familiar with
fundamentals of this kind. It may well be
the experience of Jacek Hennel and Jacek
Klinowski that only too many are not.
And I must admit that the authors’
overview and judgement are very likely
quite correct. Therefore, let us admit that
there is a need to explain such fundamentals simply and exactly. Does the book
fulfill the promise?
It starts with a chapter of 42 pages on
the “Elements of Quantum Mechanics”.
It is supplemented by five appendices explaining topics from “Complex Numbers” to “Sinusoidal Operators.” This is
now the third recent book on N M R which
I have read in which the authors assume,
on the one hand, that they must provide
an introduction to complex numbers and.
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