Synthesis,characterization, and electrochemistry of monophosphine‐containing diiron propane‐1,2‐dithiolate complexes related to the active site of [FeFe]‐hydrogenases |
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Authors: | Hui‐Min Lin Jian‐Rong Li Chao Mu Ao Li Xu‐Feng Liu Pei‐Hua Zhao Yu‐Long Li Zhong‐Qing Jiang Hong‐Ke Wu |
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Abstract: | Five monophosphine‐substituted diiron propane‐1,2‐dithiolate complexes as the active site models of [FeFe]‐hydrogenases have been synthesized and characterized. Reactions of complex [Fe2(CO)6{μ‐SCH2CH(CH3)S}] ( 1 ) with a monophosphine ligand tris(4‐methylphenyl)phosphine, diphenyl‐2‐pyridylphosphine, tris(4‐chlorophenyl)phosphine, triphenylphosphine, or tris(4‐fluorophenyl)phosphine in the presence of the oxidative agent Me3NO·2H2O gave the monophosphine‐substituted diiron complexes [Fe2(CO)5(L){μ‐SCH2CH(CH3)S}] [L = P(4‐C6H4CH3)3, 2 ; Ph2P(2‐C5H4N), 3 ; P(4‐C6H4Cl)3, 4 ; PPh3, 5 ; P(4‐C6H4F)3, 6 ] in 81%–94% yields. Complexes 2 – 6 have been characterized by elemental analysis, spectroscopy, and X‐ray crystallography. In addition, electrochemical studies revealed that these complexes can catalyze the reduction of protons to H2 in the presence of HOAc. |
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Keywords: | diiron propane‐1,2‐dithiolate electrochemistry monophosphine ligand synthesis X‐ray crystallography |
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