Synthesis, characterization, and electrochemistry of five diiron propane-1,3-dithiolate complexes with substituted phosphine ligands

In this paper, five diiron propane-1,3-dithiolate complexes containing substituted phosphine ligands were prepared and structurally characterized. Treatment of [Fe-2(CO)(6)(?-SCH2CH2CH2S)] (1) with a monophosphine ligand methyl diphenylphosphinite, ethyl diphenylphosphinite, 4-(dimethylamino)phenyldiphenylphosphine, tris(2-methoxyphenyl)phosphine, or tris(4-chlorophenyl)phosphine in the presence of Me3NO?2H(2)O as the decarbonylating agent gave the corresponding phosphine-substituted analogues [Fe-2(CO)(5)(L)(?-SCH2CH2CH2S)] [L?=?Ph2POCH3, 2; Ph2POCH2CH3, 3; Ph2P(4-C6H4 NMe2), 4; P(2-C6H4OCH3)(3), 5; P(4-C6H4Cl)(3), 6] in 73?93% yields. Complexes 2?6 have been characterized by elemental analysis, spectroscopy, and X-ray crystallography. Additionally, electrochemical studies have shown that 2?6 can catalyze the reduction of protons to H-2 in the presence of HOAc.