In this paper, three diiron butane-1,2-dithiolate complexes have been prepared and characterized. Treatment of the starting complex [Fe-2(CO)(6){mu-SCH2CH(CH2CH3)S}] (1) with a monophosphine ligand tris(2-thienyl)phosphine, tris(4-trifluoromethylphenyl)phosphine, or 4-(dimethylamino)phenyldiphenylphosphine and Me3NO center dot 2H(2)O as the decarbonylating agent gave the target products2-4in 75-91% yields. These complexes have been characterized by elemental analysis, IR, NMR spectroscopy, as well as by X-ray crystallography. Moreover, the electrochemical properties of complexes3and4were investigated by cyclic voltammetry.