26  Mechanisms of reactions in solution

Abstract

This year has seen the first Dalton Discussion in Inorganic Reaction Mechanisms. 1 This was an extremely interesting development. The overall theme was Inorganic Reaction Mechanisms: insights into chemical challenges and there were Dalton Perspectives papers in each of the themes: Applications of advanced experimental techniques, Advanced computational techniques, Small molecule activation, homogenous catalysis, Electron and energy transfer processes and Bioinorganic applications. These are to be found in the special March issue of Dalton and form a very good in-depth overview of the subject. The sessions on advanced instrumental and computational techniques covered the areas which will undoubtedly have a major effect on inorganic reaction mechanisms in the future: one by eventually allowing routine rate measurements of faster and faster reactions and the other by providing the theoretical background to the subject.As in previous years this review does not cover mechanisms of heterogeneous or solid state process, homogeneous catalysis of organic reactions, fluxional, electrochemical and photochemical processes, redox reactions involving organic substrates or organic reactions of the p-block elements.The fundamentals of theoretical modelling techniques used to calculate molecular energies and rate parameters for inorganic reactions have been described 2 and the phenomenon of so-called "phantom activation volumes" has been investigated and shown to be real activation volumes. 3 Redox reactions Long range electron transferReviews have appeared on aspects of charge-transfer processes in DNA, 4 the application of high pressure techniques to electron transfer reactions particularly in proteins and related species 5 and a theoretical analysis of donor-acceptor electron transfer, particularly super-exchange and thermally activated, mechanisms involving linear molecular bridges has appeared. 6 Electron transfer rates between the non-covalently bound flavine group at the active site to the surface of the protein in flavocytochrome c 3 from Shewanella frigidimarima