Polyhedron Vol. 11, No. I, pp. 139-140, 1992 Pergamon Press plc. Printed in Great Britain

Metals and Ligand Reactivity. By E. C. Constable. Ellis Horwood, Chichester, 1990, ISBN O-l 3-57222- 2,246pp.

Every coordination chemist who uses metal ions as tem- plates for ligand synthesis or who studies how metal ions influence the reactions of organic molecules will enjoy reading this well-written book. They will also certainly learn something new as well, because the author’s wide ranging sympathies enable him to bring a clear under- standing of many different concepts to guide the reader through a very diverse but slightly neglected area of great

interest. After surprisingly elementary accounts of theories of

bonding and reaction mechanisms, but not of acid-base behaviour, are admirable and full descriptions of how ligands change in structure and bonding on coordination, and how carbonyl compounds and other ligands react with nucleophiles and electrophiles.

These basic ideas are used to interpret template reac- tions, macrocyclic complex formation, reactions of het- eroaromatic ligands and ligand oxidation reactions. On the way we learn about such awkward problems as whether sulphur ligands will alkylate or dealkylate, which metal ions to select for a template reaction and what really happens when dipyridyl complexes are hydrolysed. The subtle thermodynamic aspects of the macrocyclic effect are very clearly explained. The book ends with a short chapter (“Envoi”) about biochemical ligand reac- tions but there is no attempt to cover this vast subject in

depth. This is not a reference book after the pattern of multi-

author multi-volume productions, and should not be used to look up particular points. The awful index would be no help anyway, but the whole topic is explained as a unity and the way to use the book is to read all the way through to achieve a general understanding of the subject and to appreciate the sort of thought processes that are involved. It will be specially suitable for new graduate students or others approaching the field for the first time.

Inevitably in a short book there are aspects omitted which one would have liked included. There is very little on experimental methods, so newcomers to the field might not know just how some results are established. Unfortunately, most of the rather few references are to reviews rather than the original literature and it will be hard for novices to find the best papers on, for example, crown ether synthesis.

Camera-ready production has been used. The large print is easy to read and most, but not all, the diagrams are very clear, but these and the equations are not num- bered so it can be tricky to locate the exact one the text is referring to. The proof reader should have another

BOOK REVIEWS

look at it, especially on pages 62 and 156, and the word “facile” appears when what the author really means is

“easy”. Nevertheless, these criticisms of detail do not seriously

detract from a warm welcome for a timely book which I hope will generate renewed interest in ligand behaviour and synthesis. It bears out Samuel Johnson’s dictum that much may be made of an organic chemist if he be

caught young enough.

Department of Chemistry PETER THORNTON Queen Mary and Westfield College Mile End Road London El 4NS, U.K.

Gmelin Handhook ; Molybdenum Suppl. Vol. B6 (Compounds with Cl, Br, I). Springer-Verlag, Heidelberg, 1991, ISBN 3-540-93619-X, 303 pp., DM 1,660.

The Gmelin Institut’s updating of their molybdenum series continues with their house authors’ production of a typically thorough volume on halide compounds. The chlorides have already featured in an earlier issue, and it is unfortunate that people with special interests in molybdenum halides have therefore to use two volumes. So anyone who is rich, or who has a rich patron, can now find the information up to 1988 on all these compounds.

The systematic Gmelin ordering of material mostly makes it easy to find the compound you want, but some complexes such as [MoO&l,(py),] are elusive. I was sur- prised to encounter [IMo~O~~]~-, which does not contain an Mo-I bond. Here the Gmelin convention seems to depart from common sense, which would put all the heteropolyanions together. Nevertheless, this volume is easier to use than some others.

One of the delights of browsing in Gmelin is to find thorough treatment of techniques you might not often use. There are plenty of phase diagrams and NQR and photoelectron data and plenty of clear tabulations of various basic spectra. If different values of some measure- ment have been found, both will be recorded here, and it is up the reader to sort it out. Similarly, there is plenty of detail about the preparation of MOO&I,, but no guid- ance as to which is the best method.

If you have the earlier series of Gmelin volumes on molybdenum, don’t throw them out, because you’ll need them to find anything earlier than 1935. Similarly you’ll need to look up separately anything in the last 3 years. That seems rather a long time lag, and I wonder if the Gmelin Institut have considered issuing their work on- line.

139

140 Book Reviews

The modern layout and the English language make the new volume one much easier to use, than its predecessor, but do be careful when you look up the citations because they are broken up in little bits and you can find yourself looking up the wrong list if you’re not careful.

Reviewing part of Gmelin is like reviewing C-D in a telephone directory. The information is all there, and that’s it. You’re not tempted to browse through the phone book, but you are with this Gmelin, because mol- ybdenum chemistry is so interesting. Much of the value of this volume will come from people who looked up one thing and found another which was more interesting. So if you have some spare MOO,, have a look in here and you’ll soon have a bright idea of what to use it for.

Department of Chemistry PETER THORNTON Queen Mary and Westfield College Mile End Road London El 4NS, U.K.

Gmelin Handbook of Inorganic Chemistry, 8th edn. Fe Organoiron Compounds. Part B16a. By W. Petz, edited by J. Faust and J. Fiissel. Springer, Berlin, 1990, ISBN 3-540-93622-X, xi + 263 pp, DM 1421. Part B16b. By H. Schumann and C. Weber, edited by J. Faust and J. Fiissel. Springer, Berlin, 1990, ISBN 3-540-93614-9, xi+ 193 pp, DM 690.

This latest volume in the treatment of mononuclear iron compounds has been published slightly out of sequence, as volume B17 has already appeared. What is remarkable is that the two parts have literature coverage up to mid- 1990, and mid-1989, respectively (with, as usual, some more recent data) ; the rapidity of publication does great credit to those involved.

The first part, B16a, is mainly concerned with C,R,Fe

carbene complexes. As such, it is a testimony to how rapidly carbene complexes have become everyday organ- ometallics ; the compounds examined in this section are mainly of the type [C5R,(2D)2Fe=CR’R2]+ (where ‘D represents a two-electron donor), or the related neutral species C5RS(*D)XFe=CR’R2. These occupy no less than 193 pages of the volume, followed by a short section on the related vinylidene complexes. Most of the compounds considered are 18-electron species, of course, but those known 17- and 1Pelectron radicals also get a mention. Part 16b is dedicated to compounds with one pentahapto ligand and additional two-electron donors. Many of these compounds are heterometallics and even include some two-iron systems where the irons are not linked and thus do not fall within the purview of series C. One of the largest sections is devoted to ferradicarbaborane systems and this is particularly valuable as the first review of this area for some years. These compounds have an interesting redox chemistry as ferrocene/ferrocenium analogues, so that a number of, formally, iron(II1) para- magnetic species are known ; a number of species where iron and cobalt are bound to the same carbaborane cage have been synthesized. Apart from carbaboranes, other heterometallic systems discussed in this volume involve metals like nickel and rhodium linked to iron through a wide range of bridging ligands.

As usual, each family of compounds has synthetic routes carefully analysed and tabulated, with all relevant data-especially spectroscopic results-listed for each compound. Clear structural diagrams are given; crystal structures are accompanied by textual commentary. Each section is accompanied by a handy review of the review literature, and there are the customary ligand and empiri- cal formula indexes that make finding the desired com- pound relatively easy.

Felixstowe College Felixstowe IPII 7NQ, U.K.

SIMON COlTON