Synthesis, structure and electrochemical property of diphenylacetypene-substituted diiron azadithiolates as active site of Fe-only hydrogenases

The model complexes 1–3 of functionalized azadithiolate (ADT)-bridged Fe-only hydrogenases, [Fe2(Co)6(μ-ADT)C6H4CCR] [R = C6H4NO2-4 (1), C6H5 (2), C6H4OCH3-4 (3)] have been synthesized in high yields under mild conditions by using Sonogashira reaction. Spectroscopic study and X-ray crystal structural analysis of 1 demonstrate that the model complexes retain the butterfly structure of 2Fe2S model analogues. The intermolecular C–H⋯O, C–H⋯π hydrogen bonding and π–π interactions play important roles in molecular packing of 1. In the presence of HOAc, complex 1 features the catalytic electrochemical proton reduction.

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