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Ketenes. By T. T. Tidwell

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Everything You Wanted to Know about Ketenes but Were Afraid to Ask
Ketenes. By 7: 7: Tidwell. Wiley, New
York, 1995. 665 pp., hardcover
E 70.00.-ISBN 0-471-57580-1
Following earlier works on ketenes,
notably the classic monograph by
Staudinger (1912) and the well-known reviews by Patai (1964 and 1980) and in
and 1993), we now
have a new up-todate monograph by
Tidwell. The first
part (51 pp.) is concerned with the
structure. bonding,
and thermochemistry of ketenes. Aspects covered in the
first chapter include
orbital treatments and the latest a b initio
methods. and energy calculations related
to protonation, substituent effects, and
stabilization of fulvenones and fulvenes,
with detailed tables where appropriate.
This is followed by a chapter on structure
determination. in which experimentally
determined bond lengths and angles are
compared with calculated values. Tables
giving CC. C O and C F bond lengths and
angles optimized by HF/6-31 G * calculations are included. These are followed by
spectroscopic and physical data, including 13C and ' H NMR data for a large
number of ketenes (and some recently
measured " 0 chemical shifts), data from
UV and photoelectron spectra, and IR
spectra (including tables comparing observed and calculated CO band positions). The chapter ends with data on
dipole moments, mass spectra, and gasphase ion chemistry, including some very
recent results.
This section contains book reviews and a list of
new books received by theeditor. Book reviews are
written by invitation from the editor. Suggestions
for books to be reviewed a n d for book reviewers
are welcome. Publishers should send brochures o r
(better) books to the editorial office: Redaktion
Angewandte Chernie. Postfach 1011 61, D-69451
Weinheirn. Germany. T h e editor reserves the right
of selecting which books will be reviewed. Uninvited books not chosen for review will not be returned.
A n . w i . C/zern I f i t E d E f 1 ~ /1996,
35,N o . 18
The second part (47 pp.) describes the
preparation of ketenes, starting with the
classical synthetic routes. In addition to
the best known routes (thermolysis of
diketenes, pyrolysis of carboxylic acids
and anhydrides, and the methods starting
from acyl halides, esters, a-halogenated
carboxylic acids, or diazoketenes), the author describes recently developed photochemical and thermolytic methods, and
syntheses starting from alkenylcarbenemetal complexes.
The following section is the longest (294
pp.), and contains detailed descriptions of
all types of ketenes, with numerous tables
listing the methods of preparation, CAS
numbers, and key literature references.
The types of compounds covered include
C-substituted ketenes (substituents: aryl,
alkyl, alkenyl, alkynyl, cyano, cyclopropyl, acyl, imidoyl, cumulenyl, and fulvenones), N-, 0-,and halogen-substituted
ketenes, Si-, Ge-, Sn-, P-, As-, S-, and
metal-substituted ketenes, bisketenes,
ketenyl radicals, anions, and cations, and
lastly cumulenones. The value of the book
lies largely in this important central part.
The last part (211 pp.) deals with the
reactions of ketenes (oxidations, reductions, photochemical and thermolytic reactions, nucleophilic and electrophilic additions to ketenes, free radical reactions,
and polymerizations. As expected, considerable space is given to cycloaddition reactions of ketenes. with particular emphasis on the [2 + 21-cycloadditipns originally
discovered by Staudinger, the [3 21- and
[4 + 21-cycloadditions, and intramolecular
cycloadditions, e.g. involving the carbony1 groups. The preparative methods
described are accompanied by semiempirical and ab-initio calculations, discussions
of the role of transition states, and stereochemical considerations. A separate subsection ( is devoted to the mechanism of the addition of ketenes to alkenes;
this includes tables listing rate constants
for the reaction, and results from MP2/631 G* and AM1 calculations of the transition states. The chapter ends by' describing cycloadditions to N = N, N = 0 and
N = S = 0 groups. 1,3-Dipolar and
[4+ 21-cycloadditions offer a route to
many interesting types of heterocycles
with a variety of applications. Intramolec-
'p VCH Vcrlugsgesellschuft mhH, 0-69451
Weinheim, 1996
ular cycloadditions are attracting growing
interest as novel synthetic stages, and
have been discussed in three recent reviews containing recent examples of their
use. The section of this book on nucleophilic additions includes a useful discussion of theoretical aspects (calculations of
energy profiles and of hydration kinetics).
Wittig reactions of ketenes yield allenes.
Aza-Wittig reactions are only mentioned
briefly, and it would have been useful to
give more references on these.
I found very few errors in the monograph. It is definitely recommended, especially for its treatment of theoretical ideas
and for the central chapter on the different types of ketenes with many informative tables. It lists over 2500 literature references, which are arranged in a clear and
readily accessible form under the individual section headings. The index is rather
meager, and it could have been enlarged
to great advantage by filling the six blank
pages at the end of the book. The structural formulas drawn by Pat Woodcock
are large and clear; however, they are not
always accurate, and the use of different
styles of formulas and standards within a
scheme is rather clumsy and inappropriate for a book in this price class, especially
since better formula-drawing programs
than ChemDraw are now available (e.g.,
ChemWindow) .
To summarize, by its lucid, well-written, and well constructed presentation this
book provides a quickly assimilable and
authoritative introduction to, and up-todate treatment of, the chemistry and theoretical aspects of ketenes. It can be thoroughly recommended for everyone involved in academic or industrial research
with an interest in this class of compounds.
Heinrich Warnhoff
Institut fur Organische Chemie
und Biochemie
der Friedrich-Wilhelms-UniversitatBonn
Bonn (Germany)
OS70-0833~96/3518-2153$ 15.00+ 25jO
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