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Book Review Synthesis of Lanthanide and Actinide Compounds. Edited by G. Meyer and L. R. Morss

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ed by a large number of illustrative figures, energy-level diagrams, numerous references and cross references, and extensive author and subject indexes. The book presents basic
physical concepts in simple terms with little formalism and
numerous experimental examples not easily found elsewhere
in such breadth. As such, it provides an interesting and comprehensible introduction for the newcomer to this fascinating field and a valuable source of information for the specialist. However, the readership the book deserves could be
limited by its prohibitive price.
Hans Heitele
Institut fur Physikalische und Theoretische Chemie
der Technischen Universitat Miinchen,
Garching (FRG)
The Chemistry of Enols. (Series: The Chemistry of Functional Groups; Series editor: s.Patai). Volume editor: Z . Rappoport. Wiley, Chichester, 1990. xvi, 823 pp., hardcover
€ 195.00.-ISBN 0-471-91720-6
The addition to the Patai series of a volume treating enols
as a functional group in its own right is clearly warranted by
the revolutionary recent advances achieved in the direct
investigation of enol chemistry. The editor of this volume
has succeeded in engaging leading proponents of recent
developments, thus providing a highly competent and informative account of all the aspects usually covered in the series, namely preparation, structure, and reactivity. Personal
views given by the individual authors provide a vivid presentation of a lively research area from different standpoints. As
a consequence, there is some reiteration of material in different chapters, but, overall, the editor and authors have
achieved a consistent and comprehensive presentation of the
chemistry of enols. Literature coverage is up to 1988 (in part
1989)and contains nearly 2500 references as well as extensive
author and subject indexes providing easy access to up-todate information. A majority of the references cited are from
the last decade, but important early work starting from
Erlenmeyer’s first contribution to enol chemistry in 1875 is
also included. The chemistry of enolates and enol ethers is
deliberately excluded.
Chapter 1 on “Theoretical Calculations” by Y Apeloig
provides an exemplary description of the fruitful interactions
between state-of-the-art theoretical methods and current experimental research. In Chapter 2 J. P. Guthrie derives increments for the Benson group additivity scheme from the
presently available data, and shows how reliably these allow
one to estimate thermodynamic parameters of enols. Chapter 3, “The Chemistry of Ionized Enols in the Gas Phase” by
F. TureEek, discusses the reversal of keto-enol equilibria in
radical cations. In Chapter 4 on “NMR, IR, Conformation
and Hydrogen Bonding” by B. Floris the emphasis is on
systems with substantial equilibrium concentrations of two
or more tautomers; the chapter includes a comprehensive
compilation of spectral data as well as studies of the effects
of solvent, substituents and temperature on equilibria. In
Chapter 5 methods for generating unstable enols in pure
form or in higher than equilibrium concentrations are presented by B. Capon. In Chapter 6 reliable keto-enol equilibrium constants are compiled by J. Toullec, and the merits
and limitations of various methods for determining these
data are critically reviewed. Old and new insight into the
kinetics and mechanism of enolization and ketonization is
reviewed by J. R. Keefe and A. J. Kresge (Chapter 7). Ernphasis is laid on new developments in monitoring ketonizaAngew. Chem. Inl. Ed. Engl. 31 (1992) No.1
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tion reactions in aqueous solution, general-acid and generalbase catalysis, isotope effects, and the pathways of the “uncatalyzed” reactions in protic solvents. Isolable and relatively stable simple enols are discussed by H. Hart, Z.
Rappoport and S. E. Biali in Chapter 8. As “simple” enols
they consider those lacking stabilizing functional groups
such as CO in the P-position, in particular the kinetically
stabilized aryl-substituted enols of the type studied by Fuson
in the early forties. Chapter 9 on “Photochemical Reactions
Involving Enols” by A. C. Weedon covers the numerous reactions which lead to the formation of enols as primary
products, as well as the photoreactions of enols themselves.
In Chapter 10 the scarce experimental data on enols of carboxylic acids and esters are reviewed by A. F. Hegarty and P.
O’Neill. In “The Biochemistry of Enols” (Chapter 11) J. P.
Richard focusses on the biochemical reactions of carbonyl
compounds which proceed through enol or enolate reaction intermediates, excluding reactions of the stable enol
Vitamin C. Unstable tautomers can sometimes be stabilized
by complexation; the properties of transition metal-enol
complexes are covered by D. Milstein in Chapter 12
“Organometallic Chemistry of Enols”. Experimental data
on “Structural Chemistry”, mainly from single crystal X-ray
measurements on isolable enols, are compiled and discussed
by G. Gilli and V. Bertolasi in Chapter 13.
The Patai series needs no recommendation as an indispensable source of comprehensive, critical and up-to-date
information. It is clearly a must for any chemical library.
Unfortunately this situation is being exploited by the publishers: the astronomical price of this volume will discourage
most researchers from purchasing their own copy.
Jakob Wirz
Institut fur Physikalische Chemie
der Universitat Base1 (Switzerland)
Synthesis of Lanthanide and Actinide Compounds. Edited by
G. Meyer and L. R. Morss. Kluwer Academic Publishers,
Dordrecht, 1991. xvi, 367 pp., hardcover HFI 220.00.ISBN 0-7923-1018-7
This compendium of invited reviews is the second in a
series of “Topics in $Element Chemistry” edited by Shyama
P. Shinha, the first having appeared some six years ago,
entitled “Americium and Curium Chemistry and Technology”, edited by Edelstein, Navratil, and Schulz. Meyer and
Morss have assembled an outstanding array of contributions
from several of the more noteworthy contemporaries in the
area of synthesis off-element compounds. As they observe in
their Preface, “The history of the rare earths has entered its
third century ;transuranium elements are now a half century
old”, so we cannot expect contributions from all ofthe major
players in f-element chemistry. The fourteen contributions
do, however, contain over 1400 citations that do well to encompass much of the previous work. The goal of the editors
and authors to compile a review of “tried and true” synthetic
techniques has been achieved. Since no single volume of
synthetic reviews can ever be complete, we should anxiously
await the next volume. What follows are some brief comments on each of the fourteen sections.
John Haschke of Rockwell International presents a very
detailed synopsis of Actinide Hydride synthesis in which he
includes an extensive review of kinetics. An additional section concerning the safe handling of hydrides and reduced
actinides was a welcome sight. So often in the literature we
neglect the “obvious” safety concerns. A very detailed sec-
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tion describing the synthesis of hydrides follows, with only a
few noticeable printing errors such as “10 bar” where the
author meant “I0 pbar”, presenting a minor technical problem if one is concerned with storing An-H compounds.
Overall, this section provides a very thorough synopsis of
current synthetic techniques.
Bernd Miiller remarks “...only such routes have been selected that lead to the purest samples of fluorides”, in the
beginning of his section on Lanthanide Fluorides. This review, although perhaps not as detailed in background material as others, emphasizes the cleanest routes to a variety of
lanthanide fluorides. Miiller has certainly provided the reader with a number of quality synthetic techniques.
The very thoroughly researched review of Actinide Fluorides coauthored by Nigel Freestone and John Holloway of
Northampton and Leicester, Great Britain, respectively,
sports a host of citations numbering well over 400. This
review contains not only synthetic techniques but most of the
crystallographic data gathered over the lifespan of actinide
fluorides research. In the seventeen sections, containing
twenty-eight tables, a gallant attempt has been made to include all of the available examples of each of the oxidation
states of the actinides and the plethora of compounds
therein. It should be noted that this volume has been limited
to actinide fluorides; Meyer and Morss would have us wait
until the next volume for the other actinide halides together
with the lanthanide hydrides.
Gerd Meyer contributes three sections describing the synthesis of lanthanide halides : Binary Lnnthanide(1II) Halides,
M X , ( X = Cl, Br, I } ; Complex Lanthanide(1II) Chlorides,
Bromides, and Iodides; and Action of Alkali Metals on Lanthanide(I1I) Halides, the last being coauthored by Thomas
Schleid. These sections are a very comprehensive review of
this chemistry, a field that has been pioneered by these authors, along with Corbett, Seifert and others. They have
included detailed illustrations of their own reaction apparatus as well as a variety of useful phase diagrams and tables.
John Corbett of Iowa State University nicely complements the halide discussion in his section Conproportionation
Routes to Reduced Lanthanide Halides. Through conproportionation, Corbett, as well as Gerd Meyer and Arndt Simon,
has explored the solid state redox chemistry of the lanthanides and scandium. The highly reactive nature of the
reduced metal halides, although desirable for novel chemistry, presents several synthetic problems that Corbett has
addressed using a special tantalum containment system.
Corbett also remarks on the frustrating role of adventitious
elements in a variety of reactions, not yielding the reduced
binary metal halides, but rather a host of new centered metal
clusters-another story for another day.
The second half of the book is devoted to the synthesis of
f-element oxides, chalcogenides and pnictides. LeRoy Eyring
presents a well written review: The Binary Lanthanide
Oxides: Synthesis and Identqication. His review identifies a
variety of synthetic means to achieve the desired end. Eyring
addresses each element and its achievable oxides by including numerous phase diagrams and stability plots. This section niceIy condenses many years of oxide chemistry into one
convenient package, and will be an asset to any scientist with
a desire to study rare earth oxides.
Rudolf Hoppe and Stephan Voigt coauthor the next chapter entitled Polynary Alkali-Metal Lanthanide Oxides, beginning with a synopsis of seven synthetic caveats. They proceed
to address these points within several thorough, albeit brief,
sections that include much of their own work together with
citations from Barnighausen. Nine tables summarize major
sections of this research, and are quite detailed in reaction
106
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conditions and references. They conclude this chapter with a
glimpse into the most current and future problems in research, perhaps encouraging us to dream of new synthetic
schemes.
“This chapter describes the most appropriate synthesis ...on the laboratory scale”, begins Lester Morss in his
contribution Synthesis of Actinide Oxides. Morss ascends
through the oxidation states of each of the actinide oxides,
directing the reader to the most appropriate sources for further review. A section describing the ultramicroscale chemistry required for handling the transplutonics introduces the
reader to the complex nature of this chemistry. Although
much of this research has been buried in obscure reports, by
citing papers that are available in most good collections
Morss has delivered a chapter that affords the reader an
opportunity to explore this chemistry in detail.
Reginald Gruehn, Giessen, coauthors two chapters concerning Chemical (Vapor Phase) Transport in Lanthanide and
Actinide Oxide and Oxychloride Chemistry. Uwe Schlaffrath
coauthors the first chapter with Gruehn, dealing with the
tantalates, oxychlorotantalates and niobates of the lanthanides. This first chapter concentrates on crystal growth
techniques perfected in their Giessen laboratory. Utilizing
the vapor phase above their reaction mixtures at high temperatures, they discovered that materials of X-ray quality
could be grown in the absence of the often interfering salt
fluxes. The second chapter, coauthored by Gerhard
Schmidt, examines the thorium tantalates and niobates. The
theme of vapor phase transport prevails throughout this review, although the cited examples are limited to CI, and
NH,CI as transport agents. The reader is left wondering why
they have limited themselves to these two systems (aluminum
halides have been used successfully in zirconium halide systems). In retrospect, this was a well drafted review.
C. E. Bamberger of Oak Ridge National Laboratory has
made a valiant attempt to describe the Synthesis of Phosphates, Carbonates, Titanates and Other Metallates of the
Lanthanide and Actinide Elements, that would have needed
four separate chapters to be comprehensive. Bamberger does
warn us that this chapter is but a brief summary of current
synthetic methods, and offers citations for specific preparative routes. This section represents an updated version of the
author’s chapter in Freeman and Keller’s “Handbook on the
Physics and Chemistry of the Actinides” (Elsevier, 1985). It
is not clear whether the broad subject matter was an editorial
choice, but that is this reviewer’s only complaint.
M. Guittard and J. Flahaut of CRNS, Paris, coauthor a
well documented chapter on the Preparation of Rare Earth
SulJides and Selenides. They provide a variety of historical
and contemporary preparative routes, including seven detailed schematic diagrams of reaction vessels. They address
the preparation of monosulfides and selenides as well as the
polychalcogenide phases. A variety of crystal growing techniques are also introduced. They do not, however, clearly
distinguish the best synthetic methods from those that simply “work’.
The last chapter describes the synthesis of an important
class of compounds. J. C. Spirlet of the Institute for Transuranium Elements, Karlsruhe, discusses the Synthesis off-Elernent Pnictides. These compounds have afforded physicists
and chemists alike an opportunity to probe a variety of unusual physical phenomena. They also present an enormous
synthetic challenge owing to the high temperatures employed
and, in the case of the actinides, the obvious safety constraints.
The author provides a table of known compounds and a
variety of detailed synthetic methods. This section is worth
reading if only for the ingenious crystal growing techniques.
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A section of the scientific community has waited too long
for such a collection to be published. This chemistry has
developed dramatically since Brown’s review “Halides of the
Lanthanides and Actinides” (Wiley, 1969), which had been
one of only a very few resources for much of this chemistry.
Katz. Seaborg and Morss updated their comprehensive series on the “Chemistry of the Actinide Elements” (2nd ed.,
Chapman and Hall, 1986), but this does not contain detailed
synthetic methods for the lanthanide compounds. The
Meyer and Morss collection provides a much needed condensed review of current chemical techniques. Aside from
only a few inconsequential proofreading errors and the other
minor complaints listed above, this book is highly recommended and belongs on the shelf of every chemist studying
lanthanides and/or actinides.
Peter K. Dorhout
Department of Chemistry
Colorado State University
Fort Collins, CO (USA)
Sulphur-Containing Drugs and Related Organic Compounds.
Chemistry, Biochemistry and Toxicology. In 6 parts (Volumes t -3, each with Parts A and B). (Ellis Horwood Series in Biochemical Pharmacy). Edited by L. A . Damani.
Ellis Horwood, Chichester, 1989. Hardcover. Prices:
E 35.00 each for Vol. 1, Pt. A; Vol. 2, Pts. A and B; Vol. 3,
Pts. A and B; E45.00 for Vol. 1, Pt. B. Vol. 1, Pt. A:
167 pp., ISBN 0-7458-0215-X; Pt. B: 324 pp., ISBN 07458-0216-8; Vol. 2, Pt. A: 163 pp., ISBN 0-7458-0217-6;
Pt. B: 175 pp., ISBN 0-7458-0218-4; Vol. 3. Pt. A:
204 pp., ISBN 0-7458-0573-6; Pt. B: 280 pp., ISBN 07458-0574-4
The outstanding importance of organosulfur compounds
in many different areas of application, and especially in
modern chemical synthesis, is sufficiently well known to
need no explanation. However, the importance of such compounds in the biological field is an aspect in which the
chemist should be no less interested, when one takes into
consideration that sulfur plays an essential role in many
biochemical processes, that it is estimated to have an average
concentration in the biosphere of about 600 ppm, that most
microorganisms and plants are capable of reducing its oxidized forms (e.g. sulfate ion), and that sulfur is incorporated
into amino acids (usually as cysteine) and into the catalytic
centers of many enzymes, and has a functional role in these.
Accordingly, there have been many monographs and
books, even some quite early ones, describing the biochemistry of endogenous organosulfur compounds (for example,
L. Young, G. A. Maw: The Metabolism of Sulphur Compounds, Methuen, London 1958; D. M. Greenberg (ed.):
Metabolism of Sulfur Compounds, Academic Press, New
York 1975; J. W. Anderson: Sulphur in Biology, Arnold, London 1978; W. B. Jakoby, 0. W. Griffith (eds.): Suifur and
Suifur Amino Acids in Methods in Enzymology, Vol. 143,
Academic Press, New York 1987). On the other hand much
less attention was given in earlier publications to the sulfur
biochemistry of exogenous synthesis products, which have
only recently come into greater prominence, and are clearly
important from an ecological standpoint. The work reviewed here is aimed specifically at covering this currently
important topic, thereby filling a noticeable gap. An attempt
has been made to bring together the widely scattered information on the biochemistry of sulfur-containing xenobiotics,
i.e. synthetic agents that are used in a wide variety of appliAngew. Chem. In[. Ed. Engl. 31 (1992) No. I
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cations as agrochemicals, pharmaceuticals or other products
made on an industrial scale.
This has resulted in a collection of 46 chapters, which are
essays rather than encyclopedically arranged compilations,
in accordance with the principle that “he who has much to
offer will bring benefits to many”. The ground covered is
remarkably extensive, touching on nearly every aspect of
metabolism, of toxicity, and in general of the biochemical
fate and mode of action of synthetically produced
organosulfur compounds used in many different areas of
application. All this is covered in three volumes, each of
which is subdivided into Parts A and B. Volume 1 is devoted
to the metabolism of sulfur-containing functional groups
(with an excellent introduction by the editor to the topic as
a whole, namely “Aspects of Sulphur Chemistry, Biochemistry and Xenobiochemistry”). In Volume 2 the analytical,
biochemical and toxicological aspects of sulfur xenobiochemistry are described in detail. Lastly, Volume 3 deals
specifically with the metabolism and pharmacokinetics of
sulfur-containing drugs.
The work has involved a whole team of experts, although
it must be added that this has resulted in a lack of uniformity
of quality and in some overlapping of subject matter (admittedly with occasional cross-references). However, this does
not detract from the work as a whole-on the contrary, the
reader can benefit from the different points of view that are
presented, and must approach the reading of the work in a
comprehensive way. A wealth of literature references is provided, extending from the early years to the latest state of
knowledge. Readers familiar with the subject as well as those
seeking an introduction to it will get good value from the
work and will find that it fulfills their expectations. There is
a wealth of information and stimulating ideas, and also
much material for teaching purposes. The standard of production, paper quality, typographical layout and printing
convey an excellent impression. In brief: the work can be
confidently recommended for all libraries concerned with
chemistry, biochemistry, pharmacology and pharmaceutical
chemistry, and for the corresponding industrial establishments, and not least for reading by individual scientists.
Werner Schroth
Sektion Chemie
der Universitat Halle-Wittenberg (FRG)
Plants for Medicines. A Chemical and Pharmacological Survey of Plants in the Australian Region. Edited by D. .
I
Collins, C. C. J. Culvenor, J. A . Lamberton, J. W Loder
and J R. Price. CSIRO Publications, Melbourne, 1990.
320 pp., hardcover $70.00.--ISBN 0-643-04992-7
This book presents an overview of the pharmacologically
interesting plants of an entire continent. It summarizes the
results of a search for new drugs undertaken from 1939 to the
end of the 1980s. The motivation for this survey and for the
intensification of research in this area was the outbreak of
the Second World War. The results were initially reported in
a number of different journals and a summary of these reports was begun in 3984. Attention focused on alkaloids and
tumor inhibitors with pharmacological studies being carried
out not only in Australia but also in America in collaboration with Smith, Kline and French (SKF) and the National
Institutes of Health (NIH). The work with the NIH involved
the investigation of the antitumor properties of about 1500
species, 122 of which exhibited reproducible activities.
Verlugsgesellschaft mbH, W-6940 Weinheim,1992
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