文摘
An amide-bound [Fe4S4]3+ cluster, [Fe4S4{N(SiMe3)2}4]鈭?/sup> (1), was found to serve as a convenient precursor for synthetic analogues of the oxidized form of high-potential iron鈥搒ulfur proteins. Treatment of 1 with 4 equiv of bulky thiols led to replacement of the amide ligands with thiolates, giving rise to a series of [Fe4S4(SR)4]鈭?/sup> clusters (R = Dmp (2a), Tbt (2b), Eind (2c), Dxp (2d), Dpp (2e); Dmp = 2,6-di(mesityl)phenyl, Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, Eind = 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl, Dxp = 2,6-di(m-xylyl)phenyl, Dpp = 2,6-diphenylphenyl). These clusters were characterized by the mass spectrum, the EPR spectrum, and X-ray crystallography. The redox potentials of the [Fe4S4]3+/2+ couple, 鈭?.82 V (2a), 鈭?.86 V (2b), 鈭?.84 V (2c), 鈭?.74 V (2d), and 鈭?.63 V (2e) vs Ag/Ag+ in THF, are significantly more negative than that of [Fe4S4(SPh)4]鈭?2鈥?/sup> (鈭?.21 V).