Full understanding of a chemical change requires the identity and nature of intermediates formed between reactants and products to be identified and knowledge of the processes of bond making and breaking and of electron transfer to be established. Inorganic reaction mechanisms are thus of intrinsic interest. Moreover, they underpin our understanding of key environmental, biological, medical and industrial processes. This review of the 1998 literature does not, except for studies of particular importance or interest, cover homogeneous catalysis or redox processes involving organic substrates, organic reactions of the heavier p-block elements, or fluxional, photochemical, electrochemical, solid-state or heterogeneous processes.A new journal, Inorg. React. Mech., and a special issue of Transition Met. Chem. are devoted to inorganic mechanisms. Activation volumes in solution, models for electron transfer, the use of density functional theory and electron-transfer reactions of polyoxymetalates have been reviewed and the application of genetic-algorithm and non-linear optimization methods to the treatment of kinetic data described. Stoppedflow EXAFS has been used to study short-lived intermediates. Studies of processes on the femtosecond timescaleare noted.
Redox reactionsA series of papers on electron transfer in proteinsand a review by Marcus on theory and experiment in electron-transfer reactions have appeared in a special issue of J. Electroanal. Chem.
Long range electron transferDifferent sites on cytochrome bc are associated with oxidation and reduction, with the Fe-S protein component of cytochrome bc acting as an electron shuttle between †Dedicated to the memory of Professor Bob Hay, an esteemed friend and colleague.
