Syntheses and Characterization of Two Diiron Dithiolate Complexes with Electron-withdrawing and Elec

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Two diiron dithiolate complexes [Fe_2(CO)_6(1,8-S_2-2-CH_2OOCPhC_(10)H_5)] 1 and[Fe_2(CO)_6(1,8-S_2-2-CH_2OOCPh-4-NO_2C_(10)H_5)]2 were synthesized in high yield. The complexes have been confirmed by single-crystal X-ray diffraction and characterized by IR, UV-Vis, ~1H NMR spectroscopy and cyclic voltammetry. They contain a butterfly Fe_2S_2 core with the Fe1–Fe_2 distances of 2.5237(7) ? in 1 and 2.5125(12) ? in 2, falling in the normal range of Fe–Fe bond length(2.49 ~ 2.57 ?). The cyclic voltammetry has been used to investigate the electrochemical properties and the electrocatalytic proton reduction for 1 and 2. The complexes display reduction peaks at –1.074 V, –1.535 V(1) and –0.869 V, –1.247 V(2) vs. Fc/Fc+, respectively. With using p-Ts OH acid of different concentration, the reduction peak of complex 2 grows non-linear; on the contrary, that of complex 1 is linear with the addition of the acid. Cyclic voltammetry revealed the two complexes are good catalysts in the CH_3CN/NBu_4PF_6 solution. Two diiron dithiolate complexes [Fe_2 (CO) _6 (1,8-S_2-2-CH_2OOCPhC_ (10) H_5)] 1 and [Fe_2 (CO) _6 (1,8-S_2-2-CH_2OOCPh-4-NO_2C_ The complexes have been confirmed by single-crystal X-ray diffraction and characterized by IR, UV-Vis, ~ 1H NMR spectroscopy and cyclic voltammetry. They contain a butterfly Fe_2S_2 core with the Fe1 -Fe2 distances of 2.5237 (7)? In 1 and 2.5125 (12)? In 2, falling in the normal range of Fe-Fe bond length (2.49-2.57?). The cyclic voltammetry has been used to investigate the electrochemical properties and the electrocatalytic proton reduction for 1 and 2. The complexes display reduction peaks at -1.074 V, -1.535 V (1) and -0.869 V, -1.247 V (2) vs. Fc / Fc +, respectively. With using p-Ts OH acid of different concentration, the reduction peak of complex 2 grows non-linear; on the contrary, that of complex 1 is linear with the addition of the acid. Cyclic voltammetry revealed the two complexes are good catalysts in the CH_3CN / NBu_4PF_6 solution.
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