Catalytic Reduction of CN−, CO, and CO2 by Nitrogenase Cofactors in Lanthanide‐Driven Reactions

Abstract

AbstractNitrogenase cofactors can be extracted into an organic solvent to catalyze the reduction of cyanide (CN−), carbon monoxide (CO), and carbon dioxide (CO2) without using adenosine triphosphate (ATP), when samarium(II) iodide (SmI2) and 2,6‐lutidinium triflate (Lut‐H) are employed as a reductant and a proton source, respectively. Driven by SmI2, the cofactors catalytically reduce CN− or CO to C1–C4 hydrocarbons, and CO2 to CO and C1–C3 hydrocarbons. The CC coupling from CO2 indicates a unique Fischer–Tropsch‐like reaction with an atypical carbonaceous substrate, whereas the catalytic turnover of CN−, CO, and CO2 by isolated cofactors suggests the possibility to develop nitrogenase‐based electrocatalysts for the production of hydrocarbons from these carbon‐containing compounds.