LAUSR

Abstract Diiron azadithiolate complexes are considered as important biomimetic models for the diiron subsite of [FeFe]-hydrogenases. Here, the diiron azadithiolate complex Fe2[(μ-SCH2)2NCH2CCH](CO)6 (1), produced by the condensation reaction of Fe2(μ-SCH2OH)2(CO)6 and NH2CH2CCH, is described. Meanwhile, the corresponding phosphine-substituted diiron azadithiolate complexes Fe2[(μ-SCH2)2NCH2CCH](CO)5L (2–6) [L = PPh3, P(C6H4-4-CH3)3, P(C6H4-4-OCH3)3, P(-2-C4H3O)3, PPh2C6H11] have been successfully prepared by the reactions of Fe2(μ-SCH2OH)2(CO)5L and NH2CH2CCH. All the new complexes 1–6 were fully characterized by elemental analysis, IR, UV/Vis, NMR spectroscopy, and for 1, 3, 4, 5 and 6 by X-ray single-crystal diffraction analysis. In addition, complexes 1–6 are all found to be active catalysts for H2 production under electrochemical conditions.