Visible Light-Driven Electron Transfer and Hydrogen Generation Catalyzed by Bioinspired [2Fe2S] Complexes

Abstract
Complexes [{(μ-SCH2)2NCH2C6H5}{Fe(CO)2L1}{Fe(CO)2L2}] (L1 = CO, L2 = P(Pyr)3, 2; L1 = L2 = P(Pyr)3, 3) were prepared, which have the lowest reduction potentials for the mono- and double-CO-displaced diiron complexes reported so far. Hydrogen evolution, driven by visible light, was successfully observed for a three-component system, consisting of a ruthenium polypyridine complex, the biomimetic model complex 2 or 3, and ascorbic acid as both electron and proton donor in CH3CN/H2O. The electron transfer from photogenerated Ru(bpy)3+ to 2 or 3 was detected by laser flash photolysis. Under optimal conditions, the total turnover number for hydrogen evolution was 4.3 based on 2 and 86 based on Ru(bpy)32+ in a three-hour photolysis.

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