Interconversion between [Fe4S4] and [Fe2S2] Clusters Bearing Amide Ligands

Structural conversion of [Fe4S4] clusters into [Fe2S2] clusters has been suggested to be a fundamental process for some O2-sensing proteins. While the formation of [Fe2S2] clusters from synthetic [Fe4S4] clusters has been unprecedented, an all-ferric [Fe4S4]4+ cluster Fe4S4{N­(SiMe3)2}4 (1) was found to split in the presence of pyridines, giving [Fe2S2] clusters Fe2S2­{N­(SiMe3)2}2(L)2 (2, L = pyridines). The structural conversion between [Fe4S4] and [Fe2S2] clusters appeared to be reversible, and the thermodynamic parameters for the equilibrium reactions between 1 + L and 2 were determined. Assembly of two [Fe2S2] clusters was also induced by chemical reductions of Fe2S2­{N­(SiMe3)2}2(Py)2 (Py = pyridine), and the resultant [Fe4S4] clusters [1]− and [1]2– were found to split into two [Fe2S2] clusters by oxidation with [Cp2Fe]+ in the presence of pyridine.