Synthesis, characterization and electrochemistry of phenyl-functionalized diiron propanedithiolate complexes

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• 作者：Chang-Gong Li ; Yong Zhu ; Xing-Xing Jiao ; Xiao-Qin Fu
• 关键词：FeFe-hydrogenase ; Diiron propanedithiolate ; Phenyl-functionalized ; Synthesis ; Crystal structure ; Electrochemistry
• 刊名：Polyhedron
• 出版年：8 January, 2014
• 年：2014
• 卷：67
• 期：Complete
• 页码：416-421
• 全文大小：849 K

文摘

A dinuclear [2Fe2S] mimic, [渭-(SCH₂)₂CHC₆H₅]Fe₂(CO)₆ (1), of the active site of FeFe-hydrogenases has been synthesized from the reaction of 2-phenyl-1,3-propanedithiol with Fe₃(CO)₁₂. Displacement one or two carbonyls of complex 1 with triphenylphosphine (PPh₃) or bis(diphenylphosphino)methane (dppm) yielded [渭-(SCH₂)₂CHC₆H₅]Fe₂(CO)₅(PPh₃) (2), [渭-(SCH₂)₂CHC₆H₅]Fe₂(CO)₅(魏-dppm) (3) and [渭-(SCH₂)₂CHC₆H₅]Fe₂(CO)₄(渭-dppm) (4). Complexes 1-4 have been fully characterized by elemental analysis, mass spectrometry, IR, ¹H, ¹³C and ³¹P NMR spectroscopic techniques, and unequivocally determined by single crystal X-ray diffraction analysis. The phenyl groups are attached directly to the bridgehead-C atoms of the propanedithiolate bridge via equatorial bonds in chair conformation six-membered rings. The electrochemical behavior of 1-4 and the reduction of the proton of CF₃COOH to hydrogen, catalyzed by 1 and 3, were investigated by cyclic voltammetry.