Multi-Electron Chemistry of Two Electron Mixed Valence Complexes

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Daniel Nocera of the Massachusetts Institute of Technology is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program to conduct research on the development of photoinduced multi-electron oxidation-reduction transformations. Dinuclear inorganic complexes in which the constituent metal centers differ by two units of oxidation state will be prepared and characterized. Photoinduced reactivity of these complexes will be studied. Specific systems selected for study include the photochemical production of dihydrogen from hydrohalic acids catalyzed by a newly discovered dirhenium photocatalyst, and related materials to be synthesized. Stereoelectronic factors that account for stabilization of two-equivalent mixed-valence complexes by diphosphazanes will be investigated and insights thus gained will be applied to design and synthesis of new two-unit mixed valence complexes.The main thrust of the present proposal is on extending scientific understanding of two-electron photochemical processes and two-equivalent mixed-valence complexes, rather than on development of specific catalyic systems. However, the work has high potential of leading to future useful technological applications, such as design of energy-conversion photocycles, and activation of C-H bonds by multielectron photoredox transformations.