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Book Review Organic ChemistryЧin Color and Good The Chemistry of the Actinide Elements. 2nd Edition. Edited by J. J. Katz G. T. Seaborg and L. R

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coming more and more important for organic synthesis,
are not treated in conjunction with the analogous silicon
compounds, but quite separately, in volume 3. This would
certainly have been a help in demonstrating the advantages
and disadvantages of the use of the two classes of compounds.
Part 2 is devoted exclusively to the use (not the preparation) of certain families of organo-transition metal compounds. Fortunately the individual chapters were almost
without exception written by very competent authors,
which has been of very great benefit to the quality. The
first chapter deals with organo-iron compounds (107 pp.,
303 references), and makes brief mention of their significance as electron-transfer catalysts. There is some overlap
here with the later chapter on the use of transition metalstabilized carbocations (90 pp., 151 references), but this is
acceptable. Between the two lie expositions of organometallic complexes of rhodium (86 pp., 551 references) and
nickel (69 pp., 363 references); here too, some overlap with
individual chapters of Volume 3 can be discerned. Chapters I 1 (“Hydrogenation”, 69 pp., 665 references) and 12
(“Mechanism of homogeneous hydrogenation”, 23 pp., 90
references) are devoted to the use of organometallic compounds as hydrogenation catalysts, in which it is not only
homogeneous and heterogeneous hydrogenations with Hz
that are discussed, but also catalytic hydrogen transfer,
and-though only briefly-enantioselective
hydrogenations with the aid of chiral metal complexes. The final
chapter deals with the activation of C-H bonds in saturated hydrocarbons, including considerations of biochemical aspects (88 pp., 295 references) and of the fixation of
catalytically active organometallic compounds onto oxide
and metal supports (62 pp., 479 references). The volume
ends with a detailed author index, and a rather less detailed subject index. Whether a continuation volume will
follow, to fill the gaps that still exist at the moment, seems
to be undecided at present.
Collecting the material presented up till now must have
been a herculean task, and the editors earn great respect
for it. Apart from the arrangement of the individual chapters, which is not always successful, the presentation of results is almost without exception very effective. It is not
only the price, however, that stands in the way of the distribution of this four-volume work, but also the fact that
the even more comprehensive work “Comprehensive Organometallic Chemistry” appeared shortly before it.
Whether HartleyIPatai can compete with this remains to
be seen.
Helmut Werner [NB 903 IE]
Institut fur Anorganische Chemie
der Universitat Wurzburg (FRG)
The Chemistry of the Actinide Elements. 2nd Edition.
Edited by J. J. Katz, G . T. Seaborg, and L. R . Morss.
Chapman and Hall, London 1986. Volume 1: xii, pp.
1-886, bound. Volume 2: xii, pp. 887-1674, bound.
Price per volume L 95.00.--ISBN 0-412-10550-0 and
0-412-27370-5
The first edition preceding this two-volume work (published in 1957 and authored by J. J. Katz and G. T. Seaborg only) dates from the pioneering years of research on
the transuranium elements and has since then become by
far the best known textbook on the chemistry of the actinide elements. Thirty years ago, not only was the final eleAngew Chem. Int. Ed. Engl. 27 (1988) No. 8
ment of the actinide series (in the sense of Seaborg’s now
well-established “actinide hypothesis”) missing, but also
the existence of the preceding element, nobelium, had not
yet been fully confirmed. Now, however, in addition to No
and Lr, the transactinides with atomic numbers 104 to 110
have also been made. The new edition, notwithstanding its
unaltered title, includes not only the 15 elements AC to Lr
but all the translawrencium elements as well.
Without considering the elements Ac, Th, Pa and U
(which together account for 430 pages of the present
work), C. Keller had still managed in 1971 to describe the
chemistry of the transuranium elements in a single volume
of 675 pages. Obviously the progress which has taken
place in almost every sector of actinide chemistry has necessitated a restructuring of the old KatdSeaborg version
(506 pages), into a well-composed collection of 24 chapters
written by 33 acknowledged experts from the USA and
Western Europe. One of the four European authors is the
late Fritz Weigel (of the University of Munich).
The very comprehensive division of the material into
Part I, which is a systematic description of the individual
elements, and Part I1 which is focusing on specific properties and classes of compounds, respectively, of all the actinides, not only follows the structure of Keller’s book, but
is already discernible in the 1st Edition. The three editors
have themselves written the historically oriented introduction (Chapter 1, 11 pages), along with several other chapters, including one of particular versatility (Chapter 14, 74
pages: Summary and Comparative Aspects of the Actinides). This chapter is intended to be an introduction to Part
11, and contains short sub-sections on such varied topics as
naturally occurring transuranium elements, superconductivity, oxidation states, organometallic compounds, nuclear reactor wastes, biological effects, and the toxicology
of actinide compounds. For non-specialists Chapter 14
might in fact serve as a guide to other parts of both volumes.
More than half of Part I is occupied by Chapters 5
(uranium, 274 pages, by F. Weigel) and 7 (plutonium, 388
pages, by F. Weigel, J. J. Katz, and G . T. Seaborg). These
chapters deal in great detail with aspects of high importance for nuclear technology, e.g. the extraction of uranium and plutonium, and chemical reprocessing of nuclear
fuels. Separation techniques are described in this chapter
too, and are also treated in detail in chapter 21. Some compilations of data in the form of tables extending over several pages, e.g. on structural parameters of selected intermetallic uranium compounds (pages 235 to 241), are perhaps out of place in a book which is intended to also attract a non-specialist readership. The transeinsteinium elements, with atomic numbers 100 to 109, are treated collectively in Chapter 13 (by R . J. Silva. 32 pages), while the final chapter (Chapter 24, by G. T. Seaborg and 0 . L. Keiler,
Jr., 25 pages), is devoted to “elements of the future”, including the so-called superheavy elements.
Organoactinide chemistry, which was virtually non-existent in 1957, is here given considerable space, mainly in
Part 11. For some reason the authors of Chapter 22 (T. J.
Marks and A . Streitwieser) and Chapter 23 (T. J . Marks),
focus mainly on the 82 pages of these two chapters, on selected, and probably exemplaric, aspects of thorium and
uranium chemistry. However, chapters 3, 5, 7, 14, 18, and
20 also each include several pages on organometallic compounds, and some transuranium elements finally feature
here. Quite a lot of repetition has crept in here, e.g. on
page 368, as a consequence of the renaming of ally1 complexes to “allenyl complexes”. Other instances of overlap1111
ping between chapters in Parts I and I1 may be found,
where the material at the two locations is not mutually
complementary.
Nevertheless, the chapters in Part I1 all deal with important topics: (optical) spectra of the free atoms and ions
(Chapter 15, M . S . Fred and J. Bluise) and of ions in compounds (Chapter 16, W. T. Carnal] and H . M . Crosswhite),
thermodynamic and magnetic properties (Chapters 17 and
18, by L. R . Morss and by N. M . Edelstein and J. Goffart,
respectively), the metallic state (Chapter 19, M . V. Nevitt
and M. B. Brodsky), structural chemistry (Chapter 20, J. H .
Burns), and solution chemistry and ionic reaction kinetics
(Chapter 21, S. Ahrlund). Analytical chemistry has not
been considered however.
Thermodynamic data of the highly radioactive actinide
compounds, which are very difficult to determine, have
rarely been presented before as systematically and comprehensively as in Chapter 17. Chapter 18 contains a short introduction to the quantitative magnetochemistry of systems with strong spin-orbit coupling and similarly large
crystal field interactions, which appears suitable even for
teaching purposes; even special treatments of magnetochemistry seldom include a chapter comparable to this.
Chapter 19 deals with systems involving non-localized (itinerant) f-electrons and heavy fermions, two related concepts which are now the subject of intensive studies, and of
relevance for a n understanding of superconductivity. (One
comes across references to the superconducting properties
of actinide compounds in several of the chapters). Chapter
20, on structural chemistry, is organized too rigidly along
classical lines, and does not mention any modern structural concepts such as those dealing with the coordinative
saturation of f-element ions, nor has the structural chemistry of complexes with macrocyclic and/or large polycyclic
ligands been considered, a subject of paramount interest at
the present time. The only example given, in the section on
actinyl complexes, is the “superphthalocyanine” complex
formed by template reaction of five phthalodinitrile molecules with the uranyl cation, its structure having been elucidated as long ago as 1975. This structure is presented
once more, under its systematic name, in Chapter 5 (page
385), where e.g. crown ether complexes and their structures
are also briefly discussed. The section on organometallic
compounds in Chapter 20 fails to take into account a number of recent developments (e.g. the uranium complexes
with arene ligands which have been reported since 1971),
and could, in view of the detailed coverage provided in
Chapters 22 and 23, probably be omitted without creating
a great loss.
The very comprehensive indexes provided at the end of
each of the two volumes (59 pages of author index and 44
of subject index in total) are usually effective in directing
one to the desired material (despite there being sometimes
not enough cross-references). Admittedly though, in the
case of the famous prehistoric nuclear reactor of Gabun,
one needs to know the key word “Oklo”, or must instead
track it down in Chapter 14 (under actinide elements of
natural origin). If one is interested in finding examples of
8-coordinate cubic actinide complexes, a ligand arrangement known to be highly unfavorable for d-transition metal ions, some more searching is needed before one finds
help in Chapter 18 (page 1373), where the magnetic properties resulting from the special crystal field splitting of the
cubic [U(NCS),]“- ion is mentioned, and also in Chapter
20 (pages 1447 and 1458). Appendix I (nuclear magnetic
dipole and electric quadrupole moments) might lead one
into a fruitless search for NMR spectroscopic data, since
the first successful 235U NMR experiment carried out in
1983 is nowhere mentioned. Even in Appendix 11, with its
extensive tables of nuclear properties, we still d o not find a
chart of common nuclides for atomic numbers289, nor
Seaborg’s popular “coastal landscape” which allegorically
depicts the relative stabilities of the heaviest elements.
Apart from the inclusion of numerous molecular and crystal structures, the second edition is less richly illustrated
than the first, which contained, for example, a color chart
showing the colors of individual actinide ions, and fullpage photographs of laboratories especially equipped for
work on transuranium elements.
Despite the above comments, the transition from the
classical KatzISeaborg to the completely restructured version of this second edition has already reached a remarkably high standard in its first appearance. The books will
certainly find their way into every good-sized chemistry library, and will be consulted frequently. The three editors
conclude their preface by expressing the hope that this
new edition might also serve as a valuable source of information to all those responsible for making far-reaching decisions on the production of nuclear energy and the control of nuclear weapons.
R . Dieter Fischer [NB 863 IE]
Institut fur Anorganische und Angewandte Chemie
der Universitat Hamburg (FRG)
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