On the reduction of iron–sulphur clusters under carbon monoxide

Abstract
Multi-electron reduction of [Fe4S4(SPh)4]2– at platinum or mercury cathodes under CO at 1 atm (101 325 Pa) gives [Fe2S2(CO)6]2–via the formation of a stable tetranuclear intermediate [Fe4S4(CO)12]2–. The product, the intermediate, and [Fe2S2(CO)6] are interrelated by a sequence of electrochemically irreversible electron-transfer steps which involve chemically reversible intra- and inter-molecular coupling or cleavage of S–S bonds. Hydrogenases and nitrogenases possessing [4Fe–4S] centres are inhibited by CO but rapid interaction of the synthetic cluster with this substrate only occurs when the highly reduced [Fe4S4(SPh)4]4– state is accessed and this corresponds to a physiologically unusual reduction level.

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