title: Catalytic reduction of CN-, CO, and CO2 by nitrogenase cofactors in lanthanide-driven reactions.
abstract: 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.
authors.affiliation: Department of Molecular Biology and Biochemistry, University of California, Irvine, Irvine, CA 92697-3900 (USA).
authors.forename: Chi Chung
authors.initials: CC
authors.lastname: Lee
authors.forename: Yilin
authors.initials: Y
authors.lastname: Hu
authors.forename: Markus W
authors.initials: MW
authors.lastname: Ribbe
mesh_terms: D055162:Biocatalysis; D002245:Carbon Dioxide / Q000032:analysis / Q000378:metabolism*; D002248:Carbon Monoxide / Q000032:analysis / Q000378:metabolism*; D003486:Cyanides / Q000032:analysis / Q000378:metabolism*; D008401:Gas Chromatography-Mass Spectrometry; D006838:Hydrocarbons / Q000737:chemistry; D007454:Iodides / Q000737:chemistry*; D009591:Nitrogenase / Q000737:chemistry / Q000378:metabolism*; D010084:Oxidation-Reduction; D012493:Samarium / Q000737:chemistry*
chemical_list: D003486:Cyanides; D006838:Hydrocarbons; D007454:Iodides; D002245:Carbon Dioxide; D012493:Samarium; D002248:Carbon Monoxide; D009591:Nitrogenase; C409809:samarium diiodide
keywords: CC coupling; carbon dioxide; enzyme catalysis; hydrocarbons; nitrogenase