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 C-1-C-4 hydrocarbons, and CO2 to CO and C-1-C-3 hydrocarbons. The CC 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.