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Book Review Carboranes. By R. N. Grimes

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BOOK REVIEWS
Principles of Mass Spectrometry and Negative Ions. By
Charles E. Melton. Marcel Dekker Inc., New York 1970.
1st ed., v, 313 pp., bound $17.75.
A series of books on mass spectrometry have so far been
published dealing either with special applications (particularly in organic chemistry) or (insofar as the authors
attempt to cover the entire field) presenting the physical
fundamentals and the principles of the equipment together
with a survey of the various fields of use.
The present book, unlike those that have preceded it, is
predominantly of the character of a textbook. The author
presents a mathematically immaculate description of the
physical principles that are required for an understanding
of the function and use of mass spectrometers. Knowledge
of vector analysis and of the manipulation of differential
equations is necessary for an understanding of the subject
matter.
The history of mass spectrometry and the wide field of uses
are described briefly, but with many references, in the introductory chapter. Chapters 2 to 8 contain the mathematical
description of the physical principles of the following fields:
2. movement of charged particles in electric and magnetic
fields, 3. formation of ions, 4. mass separation (analysis), 5.
detection of ions, 6. positive ions, 7. negative ions, and 8.
secondary reactions. No references for further studies are
given in Chapters 2 to 5.
Because of the author’s evident delight in the handling of
the methods of theoretical physics, the application of the
quantum theory in the chapters on positive ions, negative
ions, and secondary reactions, e.g. in the calculation of
effective cross sections for collision phenomena and in pair
formation, is not too brief. The appendix contains tables of
appearance potentials from investigations with negative
ions, secondary reactions of negative ions, and electron
affinities of atoms and molecules.
The book should be a useful aid to advanced students of
physics and chemistry and to physicists and chemists who
wish to familiarize themselveswith the field of mass spectrometry. However, it should also find a plerp in the laboratories of pure and applied specialists.
Karl HeinBvMaurer [NB 991 IE]
Carboranes. By R . N . Grimes. Academic Press, New YorkLondon 1970. 1st ed., xiv, 272 pp., numerous formulas
and tables, bound $14.00.
The chemistry of carboranes, which were first reported in
1953, has developed very rapidly during the past 12 years.
It now occupies an independent place alongside polyborane
chemistry. As in the case of the boranes, the syntheses, the
diverse structures, and the bonding (three-center bonds,
metal n bonds) in this class of compounds are of interest to
the inorganic chemist, the organometallic chemist, and the
organic chemist alike. The present book appears at a time
when a survey of what has been achieved is of great value.
Following the examination of the most important steric
structures and the bonding in the various types of carboranes and of the latest nomenclature, nido and closo carboranes with small and medium numbers of atoms are
discussed.
Angew. Chem. internat. Edit.J Vol. 10 (1971) 1 No. I 1
The treatment concentrates on the preparative field. Most
of the book is occupied by the description of preparations
and transformations of the three isomeric C,Bl,H12 carboranes and their derivatives and of the properties of carborane polymers. The alternate conversions of the
C,B,,H,, isomers into dicarbollides C,B,H:;
and the
preparation of monocarbapolyborates are then discussed.
A section is devoted to the degraded C,B,,H,, carboranes
with integrated main-group elements (Be, Al, Ga, Ge, Sn,
P, As, Sb), and a comprehensive chapter deals with the 7~
complexes of the various carborane anions (dicarbollides
C,B,H: ;, dicarbacanastides C,B,H:;,
dicarbazapides
C,B,Hi-) with transition metals.
The up-to-date survey is supplemented by well-chosen
literature (472 references). A comprehensive author index
and an adequately detailed subject index are added. The
author’s wish “to summarize the existing literature of carborane chemistry, and to introduce the field to organic
chemists and others with little previous knowledge of the
boranes” is fulfilled.
Roland Koster [NB 992 IE]
Selective Organic Transformations,Vol. 1. By B. S . Thyagarajan. John Wiley and Sons, New York-London-Toronto 1970. 1st ed., 400 pp., numerous formulas, bound
E 9.50.
The first volume of the new series “Selective Organic Transformations”, which will appear periodically, has now been
published. This series is to present reviews on chemical
transformations in which the formation of one of many,
usually isomeric reaction products predominates. It is
intended to place the description of a plausible reaction
mechanism alongside a pure list of preparative and kinetic
data.
B. S. Thyagarajan has managed to have the eight reviews in
the first volume written by authoritative investigators. More
than 150 of the 400 pages are taken up by the nucleophilic
addition to acetylene ( S . J . Miller and R. Tanaka) and the
stereoselective addition to allenes ( M . C. Caseirio). These
reactions have only been intensively studied during the last
few years; with careful choice of the reactants, they allow
the synthesis of olefin derivatives that are otherwise unobtainable.
Two other articles deal with the asymmetric induction in
the reduction of carbonyl compounds with hydrides ( S .
Yamada and K . Koga) and the asymmetric selection by
elimination from cycloalkyl derivatives ( S . Goldberg). Both
reactions yield the stereoisomers in unequal amounts, since
the enantiomer mixtures give transition states having different free energies. The optical induction on addition of
hydrides to dissymmetric carbonyl compounds is sufficiently well known through Cram’s rule. On the other hand,
a new chapter is opened up in asymmetric synthesis by elimination. The reactions involved here are mainly the pyrolyses of sulfoxides, amine oxides, phosphine oxides, and
esters in which the loss of a chiral group leads to two “diastereoisomeric” transition states with different energies.
A . T Bottini discusses the stereoselectivity in the quaternization of tertiary amines, and R. A . Moss describes the
cycloaddition of carbenes to olefins and subsequent reac869
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