Fe3S2 cluster complexes containing aminodiphosphine ligand: synthesis, characterization, crystal structures and electrochemical properties

In this article, six new Fe3S2 cluster complexes Fe-3(mu S-3)(2)(CO)(7)[(Ph2P)(2)NR] (1-6) (R = (CH2)(2)CH3, CH(CH3)(2), (CH2)(3)CH3, CH2CH(CH3)(2), p-C6H4CCH and m-C6H4CCH) were successfully synthesized by reactions of Fe3S2(CO)(9) and the corresponding aminodiphosphines under refluxing toluene. Meanwhile, treatment of Fe3S2(CO)(9) and (Ph2P)(2)NCH(CH3)Ph afforded two new Fe3S2 cluster complexes Fe-3(mu(3)-S)(2)(CO)(7)[(Ph2P)(2)NCH(CH3)Ph] (7) and Fe-3(mu(3)-S)(2)(CO)(7)[(kappa(2)-Ph2P)(2)NCH(CH3)(Ph)] (8). Complexes 1-8 were characterized by elemental analysis, FT-IR, NMR spectroscopy, and especially X-ray crystallography. The elctrochemical properties were investigated by cyclic voltammetry, showing that they all have electrocatalytic ability for the reduction of protons to H-2.