Reactions of Coordinated Ligands

This book is aimed at graduate students and research workers in aU branches of ohemistry, who wish to gain insight into what continues'to be one of the fastest growing areas of the subject. Aonding to a metal center may stabilize a ligand towards some reagents, activate it towards others, or modify its chemical behavior in more subtle ways. AU these effects have their uses, and aU invite understanding in terms of mechanism. Thus mechanistic insight is linked to control of reaction pathways. The detailed working out of this relationship provides the central theme of the book. The effect of the metal may be electronic or steric, and may involve the energy or the entropy of activation. It may depend on changes induced in the initial state of the ligand, or on those that only arise further along the reaction pathway. It may involve one coordination site or several, and the effects may be more, or less, specific to the metal involved and more, or less, amenable to control through the other Jigands. These remarks apply equaUy strongly to the carbon-bound ligands which occupy the major part of this work, and to those attached by other atoms. Thus the reactions discussed here are relevant in such diverse areas as bulk homogeneous catalysis, stereoselective stoichiometric synthesis, and bioinorganic chemistry.