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Book Review The Organic Compounds of Magnesium Beryllium Calcium Strontium and Barium. By S. T. Ioffe and A. N

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The Organic Compounds of Magnesium, Beryllium, Calcium,
Strontium, and Barium. By S.T. Ioffe and A . N. Nesmeyanov
(Vol. 2 of the series “Methods of Elemento-Organic Chemistry”). North-Holland Publishing Company, Amsterdam
1967. 1st Edit., x, 735 pp.. many illustrations, bound, Dfl.
The book is divided into two parts which differ in their size
and treatment. The first part (650 pages) contains 18 chapters
describing the reactions of Grignard reagents with various
classes of organic compounds, as well as the preparation,
analysis, and structure of Grignard compounds. This part is
evidently based on the three-volume handbook on organomagnesium compounds (1950) by the same authors, which
has been condensed and brought up to date by the inclusion
of additional material. The second part presents a much more
detaiIed discussion of the organic compounds of beryllium
(27 pages), calcium, strontium, and barium (18 pages). The
small space devoted to these topics reflects the scarcity of
relevant investigations.
Each chapter has a comprehensive list of references. The
literature is taken into account up to the end of 1961, and
important work carried out up to the beginning of 1965 has
also been added to the translation. The volume of publications to be covered was very large (much more than 10000
being known o n Grignard compounds alone), and the
authors are to be congratulated on the care that they have
taken in this task. For many years they have been among the
leading authorities in this field. It is for this very reason,
however, that in the reviewer’s opinion they might have made
greater use of their right to criticize. For example, in the
section “Structure of Grignard Reagents” (pp. 84-93), arguments and opinions that have now been revised are listed
chronologically alongside those that are still valid. The once
amazing zsMg-exchange experiments are described in detail,
together with the (now refuted) conclusion thatiCzHSMgBr
has the structure (CZH&Mg.MgBrz (p. 88). On‘p. 91, however, with no reference to this, we find the exchange experiments with z5Mg, which led to complete equipartition, and
o n p. 90, without comment, is the remark that the “dominant
component . . . is the RMgX compound”. Some comment by
the authors as to what may now be regarded as definite and
what may not would be of great value to readers who are
unfamiliar with the subject matter.
In view of the importance of this book as a reference work,
the author and subject indexes might perhaps have been more
detailed. For example, the important keyword “reduction”
does not appear. (The book published by Kharasch and
Reinmuth in 1954 contains 30 subsidiary entries related to the
reducing action of Grignard compounds under this keyword).
The book provides those who are interested with a valuable
reference work, which fills a gap in the long-neglected handbook and monograph literature o n organometallic chemistry.
W. P. Neumann [NB 734 IE]
The Chemistry of Niobium and Tantalum. By F. Fairbrother.
Monograph 9 of the series “Topics in Inorganic and
General Chemistry”. Edited by P . L. Robinson. Elsevier
Publishing Company. Amsterdam-London-New York
1967. 1st Edit., viii, 243 pp.. 1 6 figures, 6 tables, Dfl. 50.-.
The chemistry of niobium and tantalum is currently developing rapidly. The present compilation and selection of the
existing knowledge by an expert is therefore very welcome.
The book contains a short section o n the separation and
preparation of the elements and on the physical properties of
the metals (11 pages). The author then discusses compounds
containing oxygen, starting with the oxides and proceeding
via the hydroxides, niobates, and tantalates to the complex
compounds (48 pages). The chapter o n the oxides is one of
the few that leave something to be desired. It would have been
better here e.g. not to have discussed the modifications of
Nb205 primarily in historical order, and to have given a
clearer picture of the latest position. It would also have been
useful to include the formulas and structures of the very
interesting Magneli phases in the region from 2.4 to 2.5 O/Nb.
The section o n halogen compounds (78 pp.) is very comprehensive. The importance of metal-metal bonds in the
structures of the lower halides is also clearly explained.
Further chapters deal with the hydrides (7 pages), carbides,
silicides, and borides (17 pages), the compounds of niobium
and tantalum with the group V elements (18 pages), and the
sulfides, selenides, and teliurides (13 pages). The latest developments are again included in these chapters.
The last chapter presents a survey of analytical methods
(10 pages). However, this chapter is probably intended simply
to round off the book, and it will be necessary for the analyst
to refer to specialized works.
A large number of references facilitate consultation of the
original papers. Complete coverage cannot be expected in a
monograph of this size; it is therefore all the more important
that the author selects his material well. While the essentials
have been well selected and arranged, the reader is referred
to the literature for other themes. This may be useful to the
reader, though it would be very interesting to gain a deeper
insight into the author’s views on specific problems.
H . Schafer [NB 730 IE]
Aromatic Rearrangements. By H. J. Shine. Monograph No. 6
of the series “Reaction Mechanisms in Organic Chemistry”. Edited by C . Eaborn and N . B. Chapman. Elsevier
Publishing Company, Amsterdam-London-New York
1967. 1st Edit., 405 pp., many illustrations, Dfl. 65.-.
The editors have managed to engage a n author for this book
who has himself made a n important contribution to our
understanding of the benzidine rearrangement. It is therefore
understandable that considerable space in this book is devoted to the reactions of N-substituted amino-aromatic compounds (140 pages). Three chapters also deal with rearrangements of alkylaromatic and halogeno-aromatic compounds,
aryl esters and ethers, and aromatic amine oxides. The book
ends with two sections o n base-catalyzed (Smiles, Sommelet,
and carboxylate rearrangements, von Richter reaction) and
photochemical rearrangements. Ordinary migrations of aryl
groups, rearrangements via dehydroaromatic intermediates,
and Lewis acid-catalyzed rearrangements of polynuclear
aromatic compounds are not discussed.
The author has taken into account results from more than
500 original papers and discussed them critically. For reactions whose mechanisms are not yet clarified, the present
position is shown and the possible interpretations of the
results are considered. The numerous comparisons of rearrangements are particularly valuable.
The following observations were made regarding some of the
In the discussion of the Fries rearrangement, some reference
should have been made to K . Fries, particularly since the
histories of other reactions are outlined.
Only four of the many papers on the Claisen rearrangement
by H . Schmid and his co-workers are considered. In the excellent section on the benzidine rearrangement, the author
clearly prefers the polar-transition-state theory to the x complex theory or the radical-cation theory on kinetic grounds.
In the reviewer’s opinion. there is much to be said for the
possibility, mentioned on p. 325, that both the Sommelet and
the Stevens rearrangements proceed via ion pairs. As was
shown in 1966 (reference 50a in Chapter 3), N,N’-decamethylenebenzidine (cf. p. 135), which was first described as a
monomer (reference 17, Chapter 3), has a dirneric structure.
There are few printing errors either in the text or in the
illustrations; however, some of the formulas are very small.
On the whole, this book presents a comprehensive picture of
the work o n many rearrangements of aromatic compounds
Airgew. Chrm. interntit. Edit.
, Vol. 7 (1968)
No. 9
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book, compounds, organiz, magnesium, beryllium, barium, strontium, calcium, ioffe, review
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