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)2Fe2(CO)6]. [μ-(S-NAH)2Fe2(CO)6] has been characterized by spectroscopic methods and cyclic voltammetry. Infrared spectrum of [μ-(S-NAH)2Fe2(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)2Fe2(CO)6] feature redox events that are metal-based (irreversible, Epc: − 1.13 V, − 1.60 V vs Fc/Fc+) and naphthalic anhydride centered (partially chemically reversible, Epc: − 1.99 V; Epa: − 1.90 V vs Fc/Fc+). Cyclic voltammetric analysis of [μ-(S-NAH)2Fe2(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)2Fe2(CO)6], exhibits electronic coupling with synergistic metal–ligand interactions leading to transformation of protons to molecular hydrogen.
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This project was partially supported by grants from American Chemical Society - Petroleum Research Fund, Arkansas Tech University, and NASA- Arkansas Space Grant Consortium. The authors thank other group members for their contributions to the project.
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Mebi, C.A., Labrecque, J.H. & Williams, A.A. Metalloenzyme mimic: diironhexacarbonyl cluster coupled to redox-active 4-mercapto-1,8-naphthalic anhydride ligands. Transit Met Chem 45, 577–581 (2020). https://doi.org/10.1007/s11243-020-00410-y
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DOI: https://doi.org/10.1007/s11243-020-00410-y