Abstract The non-innocent redox-active ligand, 4-mercapto-1,8-naphthalic anhydride (HS-NAH), has been used in the design and synthesis of a diironhexacarbonyl complex, [ μ -(S-NAH) 2 Fe 2 (CO) 6 ]. [ μ -(S-NAH) 2 Fe 2 (CO) 6 ] has been characterized by spectroscopic methods and cyclic voltammetry. Infrared spectrum of [ μ -(S-NAH) 2 Fe 2 (CO) 6 ] displays peaks corresponding to terminal metal CO groups (2081, 2044, 2006 cm −1 ) and peaks assigned to C=O of the naphthalic anhydrides (1780, 1740 cm −1 ). Electrochemical measurements of [ μ -(S-NAH) 2 Fe 2 (CO) 6 ] feature redox events that are metal-based (irreversible, E pc : − 1.13 V, − 1.60 V vs Fc/Fc + ) and naphthalic anhydride centered (partially chemically reversible, E pc : − 1.99 V; E pa : − 1.90 V vs Fc/Fc + ). Cyclic voltammetric analysis of [ μ -(S-NAH) 2 Fe 2 (CO) 6 ] in the presence of acetic acid show that the complex mimics the active site of [Fe–Fe]-hydrogenase by catalyzing the electrochemical reduction of protons to hydrogen with an overpotential of − 0.67 V. The bi-functional model, [ μ -(S-NAH) 2 Fe 2 (CO) 6 ], exhibits electronic coupling with synergistic metal–ligand interactions leading to transformation of protons to molecular hydrogen. Graphic abstract

中文翻译：

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金属酶模拟物：与氧化还原活性 4-mercapto-1,8-naphthalic anhydride 配体偶联的二铁六羰基簇

摘要 非纯氧化还原活性配体 4-mercapto-1,8-naphthalic anhydride (HS-NAH) 已用于设计和合成二铁六羰基配合物 [ μ -(S-NAH) 2 Fe 2 (CO) 6 ]。[ μ -(S-NAH) 2 Fe 2 (CO) 6 ]已通过光谱方法和循环伏安法表征。[ μ -(S-NAH) 2 Fe 2 (CO) 6 ] 的红外光谱显示对应于末端金属 CO 基团的峰 (2081, 2044, 2006 cm -1 ) 和指定给萘酸酐的 C=O 的峰 (1780 , 1740 厘米 -1 )。[ μ -(S-NAH) 2 Fe 2 (CO) 6 ] 的电化学测量具有基于金属的氧化还原事件（不可逆，E pc : − 1.13 V, − 1.60 V vs Fc/Fc + ）和以萘酐为中心的氧化还原事件（部分化学可逆，E pc ：- 1.99 V；E pa ：- 1.90 V vs Fc/Fc + ）。[ μ -(S-NAH) 2 Fe 2 (CO) 6 ] 在乙酸存在下的循环伏安分析表明，该配合物通过催化质子的电化学还原来模拟 [Fe-Fe]-氢化酶的活性位点氢的过电位为 − 0.67 V。双功能模型 [ μ -(S-NAH) 2 Fe 2 (CO) 6 ] 显示出与协同金属-配体相互作用的电子耦合，导致质子转化为分子氢。图形摘要