1
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

Metals and Ligand Reactivity : By E. C. Constable. Ellis Horwood, Chichester, 1990, ISBN 0- 13-57222-2,246pp

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Page 1: Metals and Ligand Reactivity : By E. C. Constable. Ellis Horwood, Chichester, 1990, ISBN 0- 13-57222-2,246pp

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