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Book Review Materials Science and Technology (A Comprehensive Treatment). Volume 5 Phase Transformations in Materials. Edited by P. Haasen

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R . H . Grubbs reports on the use of titanacyclic compounds
and alkylidene complexes in “Living Ring-Opening
Metathesis Polymerization” (ROMP) and the application of
this method to the preparation of block copolymers and
highly conjugated polymers, of which the extreme example is
polyacetylene. W Keim et al. give a wide-ranging review of
the enantioselective telomerization of 1,3-dienes using palladium and nickel catalysts, including discussions of analytical
and mechanistic aspects. A short article by H . H . Brintzinger
on chiral ansa-metallocenes, in which the stereoselectivity of
r-olefin polymerizations is explained by mechanistic arguments, is then followed by H . Fischer’s contribution on benzylidene complexes as C, sources, which is a somewhat
longer report describing their stereoselective conversion to
give cyclopropane derivatives and heterocycles. In a very
interesting and highly imaginative article D. Astruc summarizes the work of his group on “Organo-Iron Complexes in
Aromatic Synthesis”. This describes how simple cationic
complexes of hexamethylbenzene with iron are used, in a
single-pot reaction, to prepare “tentacle” molecules, and
how the benzyl sites are then activated by electron transfer
reactions to yield a wide variety of new complexes, many of
which are multinuclear. Especially worth mentioning here is
a compilation of literature references on the activation of
arenes by transition metals. The article by D . Walther et al.
describes the activation of CO, using nickel(0) complexes
and alkenes or alkynes to give nickela-cyclic carboxylates,
which can also be prepared by reacting a bipyridyl-stabilized
diethylnickel species with cyclic anhydrides. Especially interesting here are the cyclizations with alkynes leading to the
formation of the preparatively very useful 2-pyrones with
selectivities of more than 90 % ; the trimerization reaction of
the alkyne is almost completely suppressed. A description of
the use of steroid systems in cross-coupling reactions with
nickelacarboxylates and a section on the carboxylation of
C-H bonds and of imines as “reversible CO, carriers” serve
to emphasize the close relationship between organometallic
and bioorganic CO, chemistry. The next article by J. K.
Kochi on “Charge-Transfer Activation of Organometallic
Reactions” is quite long, and is of fundamental importance
to an understanding of many of the reactions of organometallic chemistry. However, the relevance to organic synthesis here is rather tenuous.
The review by H.-J. Knolker on the use of dienyliron complexes in synthesizing natural products is very well worth
reading and full of information. It is pleasing to find that a
large number of the author’s published papers, which have
appeared within a remarkably short period, are here summarized. The emphasis is again on iron in the article by P .
Eilbracht et al. ;these authors have converted cyclohexadiene
derivatives, via their complexes with Fe(CO), with insertion
of CO. into a wide variety of carbocycles, some of which are
quite complicated, and have investigated the mechanisms of
the reaction steps. G. R. Stephenson et al. are concerned with
the control of regiospecificity in alkylation reactions using
cyclohexadienyliron complexes, and the very careful and
thorough study reported here shows that there are close
relationships to alkaloid syntheses. C. P . Casey et al. summarize their recent investigations on new reactions of
organorhenium compounds, which are very interesting from
a mechanistic standpoint; they also discuss the importance
of heterobimetallic systems. J. Okudu et al. describe the ligand (3-butenyl)tetramethylcyclopentadienyl; as a ligand
with an olefinic side-chain this is capable of reversibly blocking one of the coordination sites of the metal atom in the
corresponding cyclopentadienyl complexes. The chemical
behavior with cobalt is particularly interesting here, since the
Angew. Chem. In!. Ed. Engl. 30 (1991) No. 11
0 VCH
[2 + 2 + 21-cycloadduct was formed from two alkyne molecules and the double bond of the ligand, which, however, is
irreversibly attached to the ligand. The contribution by C.
Bolm is concerned with the use of optically active bipyridines
in enantioselective synthesis; the author has alkylated aldehydes and u,fl-unsaturated ketones with varying degrees of
enantioselectivity in the presence of these chiral ligands using
palladium or nickel catalysts. In the article by K Schurig the
main preparative interest is centered on enantioselective
methods for preparing simple oxiranes. The author also discusses aspects of prochiral and chiral recognition using complexation gas chromatography. In the article by D . Hoppe we
are reminded that “organometallics” are not confined to
transition metal compounds: N,N-dialkylcarbamoyloxy
groups not only facilitate lithiation at the adjacent sites but
also, as a result of intramolecular complexation, increase the
configurational stability of the ion pairs that are formed,
which has very important consequences for enantioselective
syntheses. An industrial research team led by A . Hafner describes a fruitful combination of transition metal chemistry
with carbohydrate chemistry: by forming chiral complexes
of carbohydrates with titanium, zirconium and hafnium, the
authors were able to prepare a number of enantiomerically
pure reactive alkylating agents. In a large number of reactions this good idea yielded enantiomeric excesses and
diastereoselectivities that were in most cases very high. Last
but not least in this collection of articles, R. Noyori et al.
present a very lucid contribution on “Multiplication and
Amplification of Chirality”. Catalytic concentrations of
enantiomerically pure 3-exo-(dimethylamino)isoborneoI
(DAIB) cause alkylzinc compounds to react with aldehydes
giving secondary alcohols with ee values up to 99%. Even
when the DAIB present in catalytic amounts has an ee value
of only 14%, a product with an ee value of 98 % is obtained.
The 17 articles have been reproduced directly, which
means that the publishers have had almost no typesetting or
correction work to do. The authors too have done their work
thoroughly, and there are very few errors; in the case of the
German authors one occasionally comes across idioms carried over from the German language. It would have been
desirable in the reaction schemes to give details of yields and
reaction conditions wherever possible. The book can be recommended to everyone interested in organometallic chemistry and organometallic methods of synthesis; it is suitable,
rather in the manner ofan advanced seminar, as an introduction to the areas of work described. A cheaper paperback
edition would have been desirable.
Holger Butenschh [NB 1177 IE]
Max-Planck-Institut fur Kohlenforschung
Mulheim a. d. Ruhr (FRG)
Materials Science and Technology (A Comprehensive Treatment). Volume 5: Phase Transformations in Materials. Edited by P . Haasen. VCH Verlagsgesellschaft, Weinheim/
VCH Publishers, New York 1991. xiii, 648 pp., hardcover
DM 430.00.-ISBN 3-527-268 18-9/0-89573-693-4
This series is planned to consist of 18 volumes altogether;
by the end of this year a further six volumes will have been
published in addition to Volume 5 which is reviewed here.
One can expect this to be an exciting series when completeand the same also goes for the price. The editors ( R . W Cahn,
P . Haasen and E. J. Kramer), on behalf of the authors (of
whom there are more than 200), introduce the series as follows: “The new series is intended to mark the coming-of-age
lJerlagsgesellschaft m b H , W-6940 Weinheim, 1991
0570-0833/9ljilll-152l$3.50+.25/0
1521
of that new discipline, define its nature and range and
provide a comprehensive overview of its principal constituent themes”. The series appears at an opportune time and
fills a real gap. Can there be anyone who has not already
come into contact in some way with the field of “materials
science and technology”? This in itself illustrates the interdisciplinary nature of this now virtually “exploding” area of
science and technology. In the past we used to refer simply
to “materials science”, but often the technological and economic implications were underestimated.
It is certainly appropriate here to briefly indicate where
Volume 5, which is the first to appear, fits into the overall
series. In this way one can explain most clearly the aim of the
series and its level (and thus also the position occupied by
each individual volume). The topics to be treated in the 18
volumes are as follows: 1 . Structure of Solids, 2. Characterization of Materials, 3. Electronic and Magnetic Properties of Metals and Ceramics, 4. Electronic Structure and
Properties of Semiconductors, 5. Phase Transformations in
Materials, 6. Plastic Deformation and Fracture of Materials,
7. Constitution and Properties of Steels, 8. Structure and
Properties of Nonferrous Alloys, 9. Glasses and Amorphous
Materials, 10. Nuclear Materials, 11. Structure and Properties of Ceramics, 12. Structure and Properties of Polymers,
13. Structure and Properties of Composites, 14. Medical and
Dental Materials, 15. Processing of Metals and Alloys,
16. Processing of Semiconductors, 17. Processing of Ceramics, 18. Processing of Polymers. Thus a picture of materials
science embracing both basic research and technology is
built up.
Phase equilibria, phase transformations, transport and
diffusion processes, reactions at interfaces, decomposition
reactions, structure-forming processes, precipitations, superlattices and crystallization processes are, of course, all of
fundamental importance to materials science. The volume
reviewed here is devoted to this topic area, which is covered
in ten chapters of roughly equal length, namely: 1. Thermodynamics and Phase Diagrams of Materials: aspects covered
are chemical equilibria and Gibbs free energy, thermodynamics of solutions, binary and ternary phase diagrams (including reciprocal salt pairs), thermodynamics and the analysis of phase diagrams.- 2. Diffusion in Crystalline Solids:
this chapter discusses macroscopic and microscopic diffusion, diffusion in solid materials, and experimental methods
for determining diffusion coefficients. - 3. Statistical Theories of Phase Diagrams : topics here include phenomenological approaches, computer methods (models) and metastability. - 4. Homogeneous Second Phase Precipitation: this
chapter covers experimental methods for studying the kinetics of decomposition reactions, the morphology of precipitates, the kinetics of decomposition reactions, increasing the
particle size of primary precipitates, and numerical calculations on nucleation, growth and increasing particle sizes. 5. Transformations Involving Interfacial Diffusion : the
structures of particle and phase boundaries, diffusion (the
roles of capillary forces, chemical forces and mechanical
forces), chemically induced migration of grain boundaries,
and discontinuous precipitations are discussed. - 6. Diffusionless Transformations: here the reader learns about
mechanisms, microstructures, morphological changes, dilative and martensitic transformations, shear transformations,
techniques of investigation, and finally properties and applications. - 7. Spinodal Decomposition : this chapter discusses
separation kinetics, the equation of nonlinear diffusion,
spinodal decomposition processes, influence of cooling rates
(quenching), systems in the neighborhood of a triple point,
spontaneous growth of ordered domains, and some experi1522
6
V C H Verlagsgesellschufi mbH. W-6940 Weinheim. 1991
mental results (selected examples from the fields of metallic
alloys, glasses, ceramics, liquid mixtures and polymer mixtures). - 8. High Pressure Phase Transformations: this chapter is concerned with experimental techniques, elements of
Group IV, 111-V compounds, barium chalcogenides, cesium
halides, xenon, semimetal/semiconductor/metaltransitions,
and molecular solids (iodine, oxygen, hydrogen). 9. Atomic Ordering: here the topics are atomic configurations, domains and configuration polyhedra, ground states,
calculations of phase equilibria (by the cluster variation or
Monte-Carlo methods) and applications to real systems. 10. Solidification: the final chapter discusses first-order
phase transformations, experimental methods, dendritic
growth, orientated (directional) crystallization, and eutectic
growth.
All the chapters, including even the strongly computingorientated Chapters 3 and 9, are elucidated by describing
selected chemical systems as examples wherever possible,
thereby ensuring that the discussion is always related to real
situations. The topics are dealt with in a rigorous and concise
manner throughout; the reader is assumed to already have
some basic knowledge of the subject. Adequate and appropriate references to original papers, review articles and
books for more advanced or supplementary reading are provided. The choice of topics and their treatment are without
doubt appropriate for such an interdisciplinary field of
study.
Research groups with interests in materials science will
need to have direct access (through their institutes and libraries) not only to Volume 5 but (presumably!) to the entire
work. This certainly also applies to groups working in the
area of “basic scientific research”, whose problems and aims
are much closer to materials science than is generally recognized.
This volume can be recommended, and the further volumes in the series that are to follow will be eagerly anticipated!
Rudiger Kniep [NB 1155 IE]
Eduard-Zintl-Institut
der Technischen Hochschule Darmstadt (FRG)
High Vacuum Techniques for Chemical Synthesis and Measurements. By P . H . Plesch. Cambridge University Press, Cambridge 1989. xiii, 167 pp., hardcover E 35.00.4SBN
0-521-25 756-5
P.H . Pfesch discusses the advantages and possible applications of high-vacuum techniques in the research laboratory in a very personal style. “This book may have a slightly
old-fashioned look” writes the author in the introduction,
and he’s not wrong in saying that. Yet the book was written
by an experienced practitioner for practical use, and contains
countless tips and tricks which are difficult to find elsewhere
in comparable literature.
This book is divided into 5 sections, and is very readable
throughout. Chapter 1 (Fundamentals) covers first of all the
fundamentals of working under an inert gas, as well as the
advantages and disadvantages of different working techniques. There then follows a short section on the theoretical
principles. Section 1.3 (Essential skills and equipment) introduces the rudiments of glass-blowing, where one is advised
not to forget Murphy’s Law. In this context I felt the advice
on safety in Section 1.4 (General comments on safety) was
especially important. Various sources of hazard are mentioned here, which cannot be overemphasized (for example,
0570-0833i9ljllfl-fj22 S3S0+.2SjO
Angen. Chem. Int. Ed. Engl. 30 11991) No. 11
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