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

Nitrogenase 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. Extracted nitrogenase cofactors (M‐, V‐, and L‐clusters) catalyzed the reductions of cyanide (CN−), carbon monoxide (CO), and carbon dioxide (CO2) to hydrocarbons in organic solvents. In these reactions, samarium(II) iodide (SmI2) and 2,6‐lutidinium triflate (Lut‐H) were employed as a reductant and a proton source, respectively.