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

摘要

The model complexes 1-3 of functionalized azadithiolate (ADT)-bridged Fe-only hydrogenases,[Fe2(Co)6(mu-ADT)-C6H4C ident to CR] [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...pi hydrogen bonding and pi-pi interactions play important roles in molecular packing of 1.In the presence of HOAc,complex 1 features the catalytic electrochemical proton reduction.