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Herein, we report the synthesis and characterization of two manganese tricarbonyl complexes, Mn^I(HL)(CO)₃Br (1 a‐Br) and Mn^I(MeL)(CO)₃Br (1 b‐Br) (where HL=2‐(2’‐pyridyl)benzimidazole; MeL=1‐methyl‐2‐(2’‐pyridy)benzimidazole) and assayed their electrocatalytic properties for CO₂reduction. A redox‐active pyridine benzimidazole ancillary ligand in complex1 a‐Brdisplayed unique hydrogen atom transfer ability to facilitate electrocatalytic CO₂conversion at a markedly lower reduction potential than that observed for1 b‐Br. Notably, a one‐electron reduction of1 a‐Bryields a structurally characterized H‐bonded binuclear Mn(I) adduct (2 a’) rather than the typically observed Mn(0)‐Mn(0) dimer, suggesting a novel method for CO₂activation. Combining advanced electrochemical, spectroscopic, and single crystal X‐ray diffraction techniques, we demonstrate the use of an H‐atom responsive ligand may reveal an alternative, low‐energy pathway for CO₂activation by an earth‐abundant metal complex catalyst.