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 [Fe 2 (CO) 6 {{ µ -SC 6 H 3 (CH 3 )S}}] ( 1 ) with one equivalent of tris(3-fluorophenyl)phosphine or tris(4-trifluoromethylphenyl)phosphine in the presence of Me 3 NO·2H 2 O as the oxidative agent afforded complexes [Fe 2 (CO) 5 {{P(3-C 6 H 4 F) 3 }}{{ µ -SC 6 H 3 (CH 3 )S}}] ( 2 ) and [Fe 2 (CO) 5 {{P(4-C 6 H 4 CF 3 ) 3 }}{{ µ -SC 6 H 3 (CH 3 )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 H 2 in the presence of a weak acid HOAc. Graphic Abstract 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.

中文翻译：

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Diiron Toluene-3,4-dithiolate 与三（3-氟苯基）膦或三（4-三氟甲基苯基）膦的配合物：合成、光谱、X 射线晶体结构和电化学性质

摘要 本文合成并表征了两种二铁甲苯-3,4-二硫醇与三(3-氟苯基)膦或三(4-三氟甲基苯基)膦的配合物。[Fe 2 (CO) 6 {{ µ -SC 6 H 3 (CH 3 )S}}] (1) 用一当量的三(3-氟苯基)膦或三(4-三氟甲基苯基)膦处理六羰基络合物[Fe 2 (CO) 6 {{ µ -SC 6 H 3 (CH 3 )S}}] (1) Me 3 NO·2H 2 O 作为氧化剂的存在提供了复合物 [Fe 2 (CO) 5 {{P(3-C 6 H 4 F) 3 }}{{ µ -SC 6 H 3 (CH 3 ) S}}] ( 2 ) 和 [Fe 2 (CO) 5 {{P(4-C 6 H 4 CF 3 ) 3 }}{{ µ -SC 6 H 3 (CH 3 )S}}] ( 3 )分别为 90% 和 80% 的分离产率。上述得到的新配合物已通过元素分析、红外光谱、核磁共振光谱表征，其结构已通过单晶X射线衍射分析得到进一步证实。此外，电化学研究表明，它们可以在弱酸 HOAc 存在下催化质子还原为分子 H 2。图形摘要 通过羰基取代合成了两种二铁甲苯-3,4-二硫醇与三（3-氟苯基）膦或三（4-三氟甲基苯基）膦的配合物，并通过元素分析、光谱、X射线衍射分析和环伏安图。