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Azadithiolate-bridged [FeFe]-hydrogenase mimics with bridgehead N-derivation: structural and electrochemical investigations

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Abstract

To further develop the active site mimics of azadithiolate-bridged [FeFe]-hydrogenases, a series of new diiron azadithiolate complexes [{(μ-SCH2)2N(C6H4CH2CH2OC(O)R)}Fe2(CO)6] (R = CH2C6H4Me-p, 2; C6H5, 3; CH3, 4) bearing bridgehead N-derivation were successfully prepared by facile esterification reaction of parent complex [{(μ-SCH2)2N(C6H4CH2CH2OH)}Fe2(CO)6] (1) and different carboxyl compounds RCO2H in the presence of 4-dimethylaminopyridine (DMAP) as catalyst and dicyclohexylcarbodiimide (DCC) as dehydrating reagent. Complexes 2–4 have been fully characterized by means of elemental analysis, FT-IR and NMR (1H, 13C) spectroscopies, and especially for 2 by X-ray crystallography. Further electrochemical and electrocatalytic properties of target complexes 2–4 and reference analogue 1 were studied and compared in the absence and presence of acetic acid (HOAc) as a proton source by cyclic voltammetry (CV), indicating that they may be considered as the active biomimetic electrocatalysts for proton reduction to hydrogen (H2).

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Acknowledgements

This work was financially supported by Research Project Supported by Vanadium and Titanium Resources Comprehensive Utilization Key Laboratory of Sichuan Province (No. 2021FTSZ07), Fundamental Research Program of Shanxi Province (No. 20210302123042), and Research Project Supported by Shanxi Scholarship Council of China (No. 2021-119).

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Authors and Affiliations

  1. College of Chemistry and Environmental Engineering, Sichuan University of Science and Engineering, Zigong, 643000, People’s Republic of China

    Ming-Sheng Gui, Yu Guan & Yu-Long Li

  2. School of Materials Science and Engineering, North University of China, Taiyuan, 030051, People’s Republic of China

    Pei-Hua Zhao

  3. Vanadium and Titanium Resource Comprehensive Utilization Key Laboratory of Sichuan Province, Panzhihua, 617000, People’s Republic of China

    Yu-Long Li & Pei-Hua Zhao

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  1. Ming-Sheng Gui
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  2. Yu Guan
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Gui, MS., Guan, Y., Li, YL. et al. Azadithiolate-bridged [FeFe]-hydrogenase mimics with bridgehead N-derivation: structural and electrochemical investigations. Transit Met Chem 47, 257–263 (2022). https://doi.org/10.1007/s11243-022-00508-5

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