Abstract

A synthetic heavier p-block bismuth (Bi) complex with a rigid pincer ligand, is shown to be a Bi-based molecular electrocatalyst for proton reduction under weak acid conditions. High activity of the complex is observed in catalysis, with a icat/ip value of 95 with CH3CO2H. Experimental and theoretical studies indicate that the hydrogen evolution reaction (HER) mechanism involves generating a low-valent BiI complex and its reactivity toward acid to form a BiIII-hydride species. Subsequent protonolysis of the BiIII-hydride eliminates H2 through a heterolytic route. The HER cycling through the low-valent metal species and its hydride has been proposed previously in transition-metal (TM) centered catalysts but rarely validated in main-group catalytic systems. The finding brings insight into heavier main-group Bi-catalyzed H2 evolution and the role of low-valent main-group metal centre during catalysis.

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