Abstract

In this paper, two diiron toluene-3,4-dithiolate complexes with tris(3-fluorophenyl)phosphine or tris(4-trifluoromethylphenyl)phosphine have been synthesized and characterized. Treatment of hexacarbonyl complex [Fe2(CO)6{{µ-SC6H3(CH3)S}}] (1) with one equivalent of tris(3-fluorophenyl)phosphine or tris(4-trifluoromethylphenyl)phosphine in the presence of Me3NO·2H2O as the oxidative agent afforded complexes [Fe2(CO)5{{P(3-C6H4F)3}}{{µ-SC6H3(CH3)S}}] (2) and [Fe2(CO)5{{P(4-C6H4CF3)3}}{{µ-SC6H3(CH3)S}}] (3) in 90% and 80% isolated yields, respectively. The new complexes obtained above have been characterized by elemental analysis, IR, NMR spectroscopy, and their structures have been further confirmed by single crystal X-ray diffraction analysis. In addition, electrochemical studies revealed that they can catalyze the reduction of protons to molecular H2 in the presence of a weak acid HOAc. Two diiron toluene-3,4-dithiolate complexes with tris(3-fluorophenyl)phosphine or tris(4-trifluoromethylphenyl)phosphine have been synthesized by carbonyl substitution and studied by elemental analysis, spectroscopy, X-ray diffraction analysis, and cyclic voltammogram.

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