title: Reduction of C1Substrates to Hydrocarbons by the Homometallic Precursor and Synthetic Mimic of the Nitrogenase Cofactor.
abstract: Solvent-extracted nitrogenase cofactors can reduce C1substrates (CN-, CO and CO2) to hydrocarbons in reactions driven by a strong reductant, SmI2(E0'= -1.55 V vs SCE). Here we show that a synthetic [Et4N]4[Fe6S9(SEt)2] cluster (designated the Fe6RHH-cluster), which mimics the homometallic [Fe8S9C] core of the nitrogenase cofactor (designated the L-cluster), is capable of conversion of C1substrates into hydrocarbons in the same reactions. Comparison of the yields and product profiles between these homometallic clusters and their heterometallic counterparts points to possible roles of the heterometal, interstitial carbide and belt sulfur-bridged iron atoms in catalysis. More importantly, the observation that a "simplified", homometallic cofactor mimic can perform Fischer-Tropsch-like hydrocarbon synthesis suggests future biotechnological adaptability of nitrogenase-based biomimetic compounds for recycling C1substrates into useful chemical and fuel products.
authors.affiliation: Department of Molecular Biology and Biochemistry, University of California, Irvine , Irvine, California 92697-3900, United States.
authors.forename: Nathaniel S
authors.initials: NS
authors.lastname: Sickerman
authors.affiliation: Department of Molecular Biology and Biochemistry, University of California, Irvine , Irvine, California 92697-3900, United States.
authors.forename: Kazuki
authors.identifier: 0000-0003-1500-1332
authors.initials: K
authors.lastname: Tanifuji
authors.affiliation: Department of Molecular Biology and Biochemistry, University of California, Irvine , Irvine, California 92697-3900, United States.
authors.forename: Chi Chung
authors.initials: CC
authors.lastname: Lee
authors.affiliation: Department of Chemistry, Graduate School of Science and Research Center for Materials Science, Nagoya University , Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan.
authors.forename: Yasuhiro
authors.initials: Y
authors.lastname: Ohki
authors.affiliation: Department of Chemistry, Graduate School of Science and Research Center for Materials Science, Nagoya University , Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan.
authors.forename: Kazuyuki
authors.initials: K
authors.lastname: Tatsumi
authors.affiliation: Department of Molecular Biology and Biochemistry, University of California, Irvine , Irvine, California 92697-3900, United States.|Department of Chemistry, University of California, Irvine , Irvine, California 92697-2025, United States.
authors.forename: Markus W
authors.identifier: 0000-0002-7366-1526
authors.initials: MW
authors.lastname: Ribbe
authors.affiliation: Department of Molecular Biology and Biochemistry, University of California, Irvine , Irvine, California 92697-3900, United States.
authors.forename: Yilin
authors.initials: Y
authors.lastname: Hu
mesh_terms: D032701:Biomimetics; D003067:Coenzymes / Q000737:chemistry*; D006838:Hydrocarbons / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008958:Models, Molecular; D009591:Nitrogenase / Q000737:chemistry*; D010084:Oxidation-Reduction; D013379:Substrate Specificity
chemical_list: D003067:Coenzymes; D006838:Hydrocarbons; D007501:Iron; D009591:Nitrogenase