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Comprehensive Coordination Chemistry, 7 vols.

Comprehensive Coordiantion Chemistry: 7 Volumes The authors of the chapters are recognized workers in the field. Most of them are from the USA 3r UK but the significant number of Canadians -- among them C.J.L. Lock, FCIC, H.E. Howard-Lock, FCIC, D. Dolphin, FCIC, T. Mashiko, A. Shaver, MCIC, P.A.W. Dean, MCIC, M.A. Jamieson and N. Serpone -- attest to the quality and international recognition of the work that has been going on in this country. Each section is well-referenced, with citations through about 1985. Approaches taken to presenting the material vary with the author's area of expertise, but most sections cover basic aspects of structure, bonding, syntheses, spectroscopic and other physical properties, and reactions. Dates are often tabulated and structural diagrams and reaction schemes are plentiful. In cases where major reviews of previous work are readily available (as they are for ammine complexes), these are cited and the authors restrict themselves to more recent work.

Material in volumes 2-5 is presented in the order dictated by the periodic table. This logical approach has the occasional startling consequence: the volume on ligands begins with Phil Dean's chapter on mercury as a ligand, which is scarcely the entry point a coordination chemist would choose!

In a series such as this, some overlap of coverage is bound to happen. This is generally all to the good; S.H. Laurie's chapter in volume 2 on naturally occurring ligands (30 pages) seems much to brief, but M.N. Hughes in volume 6 makes up for this with more than 200 pages devoted to coordination compounds in biology, and P.A. Williams, MCIC, (also in volume 6) considers the role of naturally occurring ligands in geochemical transport and ore formation. D.St.C. Black has chapters in both volumes 2 and 6 on reactions at coordianted ligands: the former organizes reactions according to type while the latter stresses the template effect and its usefulness in creating new ligands. R.W. Hay in volume 6, in a separate chapter on Lewis acid catalysis, echoes Black when he discusses imine formation. Some of the material on reaction mechanisms in volume 1 appears again in volume 2 as reactions specific to given classes of ligand are discussed. Many of the examples used in the more general volumes (1, 2, and 6) are covered again in volumes 3, 4, and 5 on the coordination compounds of each element.

Each volume has its own subject and formula index, and the indices are cumulated in volume 7. Volume 7 also contains a separate index to major reviews (more than 1,700 of them); the indexing here is by access tables organized according to topic. For example, there is a table on isomerism and fluxionality, subdivided into eight categories such as recemization, absolute configuration, and linkage isomerism. Titles are included for the reviews in addition to the author names and the usual journal citation.

The publishers claim that this set of volumes contains the most detailed account of present-day coordination chemistry available, and will serve as a reference source for years to come. This reviewer agrees; the series will take its place alongside Comprehensive Inorganic Chemistry and Comprehensive Organometallic Chemistry, thus providing an inorganic chemist with a nearly complete overview of the discipline to date.

Volume 1 begins with the historical development of coordination chemistry, beautifully summarized to 1930 by G.B. Kauffman and after that date by J.C. Bailar. D.L. Kepert's treatment of coordination numbers and geometrics, especially for complexes with bidentate ligands and mixed monodentate-bidentate complexes, follows his book on the same subject, and is logically placed as the second chapter. The most recent developments in nomenclature are covered by T.E. Sloan of Chemical Abstracts Service.

I.G. Dance's chapter on clusters and cages is intended in part to show the linkages between traditional mononuclear coordiantion compounds and Pfeiffer's concept of inorganic crystals (such as NaC1) as infinite network coordiantion compounds. The treatment is eclectic at best. Metal-metal bonded species are treated simultaneously with polynuclear complexes in which there is no evidence of metal-metal bonding. Given that such an organization lends itself well to categorizing cluster types according to geometry, one would expect that oxo ions such as [V.sub.10.O.sub.28/.sup.6-] and the Keggin- and Dawson-type structures for tung-states would at least be mentioned, and they aren't.

J.MacB. Harrowfield and S.B. Wild thoroughly discuss isomerism in coordination chemistry, from the simpler types up through the more subtle types of steroisomerism arising from constraints due to chelate or macrocyclic ring conformations. Bond stretch isomerism is not mentioned, although it seems to be well-established if not well-known (ie., see Y. Jean, A. Lledos, J.K. Burdett, and R. Hoffman, J. Am. Chem. Soc. 1988, 110, 4506).

B.N. Figgis' treatment of ligand field theory presents the basic theoretical bonding description and its consequences for spectroscopic and magnetic properties of transition metal compounds.

Five chapters on reaction mechanisms cover ligand substitution reactions (M.L. Tobe), electron transfer reactions (T.J. Meyer and H. Taube, MCIC), photochemical processes (C. Kutal and A.W. Adamson), reactions of coordinated ligands (D.St.C. Black), and reactions in the solid state (H.E. LeMay). LeMay reviews the literature on isomerization, racemization, ligand exchange, photochemical reactions and changes in coordiantion number and/or geometry, showing the solid state is not the chemical graveyard chemists suppose it to be.

The inal chapters cover aqueous and nonaqueous chemistry, C.J. Pickett and D.H. Vaughan review electrochemistry and its application to synthesis and chemistry of coordination compounds. Vaughan then describes the quantitative treatment of solvent effects on ecomplex stabilities and redox potentials. In the last chapter H.M.N.H. Irving summarizes applications of metal complexes to areas of analytical chemistry such as masking, solvent extraction, titrimetry, gravimetry, spectrophotometric analysis, and gas chromatography.

Of all the volumes in the series, volume 1 is probably most useful to the serious student or teacher of inorganic chemistry. The remainder provide excellent coverage of specific research areas.

The emphasis in volume 2 is on the ligands themselves rather than on the metal ions to which theya re attached. One finds discussions of ligand syntheses, spectroscopic transitions associated with the ligands, and properties such as the come angle (for trilkyl phosphines) and how it affects complexation ability. Of course metal complexes are discussed as well, but only to elaborate the behaviour of the ligand in a given situation.

Forty sections treat ligand whose donor atoms come from a single group in the priodic table, ligands with mixed donors, and multidentate macrocyclic ligands. Carbon-donor ligands are excluded for cyanides and fulminates; agostic bonding by C-H groups acting as two-electron donors is not covered, presumably because compounds with these kinds of interactions are treated as organometallics rather than coordination compounds. On the other hand, bonding by [H.sub.2], which is similar to bonding by C-H, is discussed in R.H. Crabtree's chapter on hydrides.

The subdivision of ligand types is logical and seems to cover practically all ligands. For example, oxygen-donor ligands include ater, hydroxide, and oxide; dioxygen, superoxide, and peroxide; alkoxides and aryl oxides; diketones; oxyanions; carboxylates; hydroxy acids; sulfoxides, amides, and amine oxides; and hydroxamates. Mixed donor atoms ligands arte subdivided into Schiff bases; amino acids, peptides, and proteins; complexones; and bidentate ligands. The only notable omission is that there is no treatment of alkyl halides as ligands, even though many complexes are known in which C-X groups are bonded to metal ions (especially when X = F).

K.B. Mertes and J.-M. Lehn have a superb chapter on multidentate macrocyclic and macropolycyclic ligands. Design principles are articulated, and then different ligand types are discussed, starting with crown ethers and working up through macropolycyclic systems. B.J. Hathawayhs chapter on oxyanions is a comprehensive catalog of all the different structural possibilities for oxyanions behaving as ligands. These chapters are typical for this volume, which is a truly excellent source for information about common and uncommon ligands.

Volume 6 is dedicated to current uses of coordiantion compounds or their applications to other fields. Nearly 400 pages (five chapters) are given over the synthetic and catalytic applications, including hydrogen production from water and oxidation of organic substrates. A. Spencer's chapter on catalytic activation of small molecules is excellent in its treatment of hydrogenation, carbonylation, hydroformylation, and other such reactions. R.W. Hay focusses on hydrolytic and other bond-breaking reactions at coordinated ligands, while D.St.C. Black looks at the template role of the metal ion in bond-forming reactions.

H.E. Howard-Lock, FCIC and C.J.L. Lock, FCIC review the therapeutic uses of metal complexes, and C.J. Jones has a section on radiophar-maceuticals. These complement M.N. Hughes' massive chapter -- almost a book in itself -- on coordination compounds in biology.

Many chapters involve the applications of metal complexes to major industrial processes: electrodeposition of metals and other electrochemical processes, manufacture of dyes and pigments, manufacture of photographic and other imaging systems, extractive metallurgy, and processing and recoery of nuclear fuels. In addition, topics likely to be of considerable importance in the future are discussed, eg., surface-modified electrodes and complexes with unusual electrical properties. Volume 6 concludes with a chapter on various commercial uses of transition metal complexes not considered in previous chapters.

Mary Frances Richardson, FCIC Brock University
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Author:Richardson, Mary Frances
Publication:Canadian Chemical News
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Date:Jan 1, 1990
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