The serious study of the reaction mechanisms of transition metal com­ plexes began some five decades ago. Work was initiated in the United States and Great Britain; the pioneers ofthat era were, inalphabetical order, F. Higgision, E.1.

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Wilkins.A larger community of research scientists then entered the field, many of them stu­ dents ofthose just mentioned. Interest spread elsewhere as well, principally to Asia, Canada, and Europe. Before long, the results ofindividual studies were being consolidated into models, many of which traced their origins to the better-established field of mechanistic organic chemistry. For a time this sufficed, but major revisions and new assignments of mechanism became necessary for both ligand sub­ stitution and oxidation-reduction reactions. Mechanistic inorganic chemistry thus took on a shape of its own.

This process has brought us to the present time. Interests have expanded both to include new and more complex species (e.g., metalloproteins) and a wealth of new experimental techniques that have developed mechanisms in ever-finer detail. This is the story the author tells, and in so doing he weaves in the identities of the investigators with the story he has to tell. This makes an enjoyable as well as informative reading.

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The sulfur-bridged dimeric dithiolato rhenium(V) chelate ( D), derived from 2-mercaptothiophenol, was monomerized to give ( M− L) in benzene upon reaction with various neutral and anionic monodentate ligands ( L) such as pyridine and its substituted derivatives, triarylphosphines, dimethyl sulfoxide, 4-picoline- N-oxide, and halide ions. The kinetic observations can readily be interpreted for all ligands by a unified mechanism in which the initial fast formation of a 1:1 ( DL) and 1:2 ( DL 2) adduct is followed by the slow monomerization of each species so formed. The use of different ligands gave insight into different steps of the same multistep mechanism. The kinetics of ligand exchange between free L and the monomeric complexes was also studied; an associative pathway has been proposed to interpret the results. The crystal structures of two new monomeric ML complexes (with L = 4-acetylpyridine and 1,3-diethylthiourea) are reported.