and E2 reactions are discussed, where frequently specific sol- vations decide the issue. However, this chapter also includes a thorough discussion of the considerably weaker effects in radical and pericyclic reactions, together with their mecha- nistic consequences. The chapter has 45 1 references.

A further chapter (45 pages) deals with solvent effects on spectral properties. Starting with solvatochromism phenom- ena (UV/VIS), the author describes effects on IR, NMR, and ESR spectra, by which it is also often possible to detect specific solvations. This provides a logical transition to linear “free energy relationships” (54 pages), which are mainly de- rived from spectroscopic data for given model systems and which, possibly just because of their empirical nature, range over an astonishingly wide field of chemical reactivity. Here too the book shows the use and limitations of the Z and ET values and AN and D N values, together with the value of multiparametric equations, some of which have only recently been developed.

An appendix gives brief information about the purifica- tion and possible applications of solvents, their spectroscopic and other physical data, and also their toxicity.

No other work currently available presents the confusing multiplicity of solvent effects as thoroughly, comprehensive- ly, and critically as this one. Furthermore, it is intended for the organic chemist who wants to interpret these effects or to use them in planning his reactions. It is hoped that the high price will not hinder a wide readership of this book.

Siegfried Hiinig [NB 481 IE]

Organometallic Mechanisms and Catalysis. By J. K. Kochi. Academic Press, New York 1978. xvii, 623 pp., $ 59.50. It isn’t very often that a reviewer has the good luck to be

asked to write a critique about a book which he intended to purchase and I was, therefore, delighted when this volume landed on my desk-particularly in view of the price.

Organometallic chemistry and homogeneous catalysis can no longer be ignored by conventional organic and inorganic chemists: many organometallic compounds have either found direct practical application (e. g. organotin- and orga- nolead compounds) or are routinely used as stoichiometric reagents in organic synthesis (e. g. organolithium- and orga- nomagnesium compounds) or are involved as intermediates in metal catalyzed organic transformations some of which now form the basis of large industrial processes (e. g. organo- cobalt- and organonickel compounds in the hydroformyla- tion and hydrocyanation of alkenes).

Although a number of reaction- or metal-specific books and reviews are available, it has become clear in the last few years that the role of organometallic species in organic syn- thesis could be profitably discussed from a unifying mecha- nistic standpoint and it is to fill this need that this book has been written.

Has the author succeeded? On the whole I think he has. He is certainly to be admired for not capitulating before the sheer volume of the material to be discussed. The book is di- vided into three related sections: part one deals with oxida- tion-reduction processes in which the metal undergoes a dis- crete change in oxidation state, part two is devoted to the chemistry of organometallic compounds with emphasis on reactions leading to cleavage of the metal-carbon bond, and part three is concerned with charge transfer interactions.

This arrangement enables a surprising amount of informa- tion to be classified while avoiding the frequently artificial distincticn between main group- and transition-metal orga- nometallic compounds. A first-class index makes it easy to

804

find relevant material. The main difficulty facing the author is that concrete evidence is often lacking for many of the ca- talytic processes being considered and, in spite of his good intentions, the discussion all too often becomes metal- specific and generalizations have to be followed by a disclaim- er. The most desirable effect which this book could have would be to stimulate further work towards greater mechani- stic uniformity.

The book will be of greatest interest to chemists involved directly with organometallic compounds and catalysis but it should also be very profitable reading for all preparative or- ganic chemists. Its greatest service will be to act as an orien- tation point in classifying new information. For me at least it will now be easier to keep an eye on what is happening in the wood while at the same time tending some of the trees.

[NB 477 IE] P. W . Jolly

The Chemistry of Functional Groups. The Chemistry of Dia- zonium and Diazo Groups. Edited by S. Patai. John Wiley & Sons, New York 1978. Part 1, xiv, 510 pp.; Part 2, xiv, pp. 511-1069; bound, together $ 130.00. The last comprehensive survey of diazo and diazonium

compounds (H. Zollinger: Diazo and Azo Chemistry) was published in 1961; the pertinent chapters of Houben-Weyl (10/3 and 10/4) were written in 1965 and 1968. The present two-volume work in the series “Chemistry of Functional Groups” is therefore most welcome.

Diazonium ions and diazo compounds do have a number of interfaces (they are related by acid-base equilibria in the aliphatic series), but differ greatly in their reactions. The two classes of compounds are therefore considered together in some of the chapters, but separately in others. The work opens with a theoretical survey ( J . B. MoJfaat) which also em- braces diazirines and diimides. Three chapters are concerned with the synthesis of diazonium salts (14, K. Schank) and of diazoalkanes and their carbonyl, phosphoryl, and sulfonyl derivatives (15, 17, M. Regitz). Further chapters are devoted to acid-base equilibria (2, V. Sthba; 6, J. F. McGarrity), structural problems (3 , S. Sorriso; 7, H. M. Niemeyer), and analytical procedures (5, D. A. Ben-Efraim). The section on thermochemistry (4, R. Shaw) does not appear very success- ful, being based on a value for the heat of formation of dia- zomethane which is most probably incorrect. Mechanistic questions are discussed with particular emphasis on photo- chemistry (9, W. Ando), electrochemistry (10, J. Fry), substit- uent effects (11, E. S. Lewis), kinetics (12, A . F. Hegarty), rearrangements (13, D. Whittaker), and the use of isotopes (16, P. J. Smith and K. C. Westaway). Special attention is fo- cused on the synthetic application of diazonium salts (8, D. S. Wulfman) and diazo compounds (18, D. S. Wulfman, G. Linstumelle, and C. F. Cooper) by two large chapters with ca. 2400 references. This is where the chemist engaged in prepa- rative work will gain well-founded information and critical suggestions concerning, for example, the choice of catalyst in the decomposition of diazo compounds.

Repetition is bound to occur in a book written by 19 authors (e.g. the Wolff rearrangement is mentioned in Chapters 3, 9, 13, and 18); and yet new aspects are often revealed precisely by such repetition. Some information turns up in unexpected places, e. g. I3C-NMR data of diazo compounds in Chapters 11 and 16, but not in Chapter 5 and regrettably not in the in- dex. Typographical errors are rare (e.g. pp. 374, 413, 607, 629, 726, 851, 855, 909,932); errors of fact are even rarer (the statement on p. 13 that diazirine is more stable than diazo- methane contradicts the heats of formation compiled in Tables 10 and 11; classification of the photochemical Bamford-Stev-

Angew. Chem. Int. Ed. En@. I8 (1Y79) No. 1 0