title: Structure and Reactivity of an Asymmetric Synthetic Mimic of Nitrogenase Cofactor.
abstract: The Mo nitrogenase catalyzes the ambient reduction of N2to NH3at its M-cluster site. A complex metallocofactor with a core composition of [MoFe7S9C], the M-cluster, can be extracted from the protein scaffold and used to facilitate the catalytic reduction of CN-, CO, and CO2into hydrocarbons in the isolated state. Herein, we report the synthesis, structure, and reactivity of an asymmetric M-cluster analogue with a core composition of [MoFe5S9]. This analogue, referred to as the Mo-cluster, is the first synthetic example of an M-cluster mimic with Fe and Mo positioned at opposite ends of the cluster. Moreover, the ability of the Mo-cluster to reduce C1substrates to hydrocarbons suggests the feasibility of developing nitrogenase-based biomimetic approaches to recycle C1waste into fuel products.
authors.affiliation: Department of Molecular Biology and Biochemistry, University of California, Irvine, Irvine, CA, 92697-3900, USA.
authors.forename: Kazuki
authors.initials: K
authors.lastname: Tanifuji
authors.affiliation: Department of Molecular Biology and Biochemistry, University of California, Irvine, Irvine, CA, 92697-3900, USA.
authors.forename: Nathaniel
authors.initials: N
authors.lastname: Sickerman
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.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: Takayuki
authors.initials: T
authors.lastname: Nagasawa
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: Kosuke
authors.initials: K
authors.lastname: Miyazaki
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, CA, 92697-3900, USA.
authors.forename: Yilin
authors.initials: Y
authors.lastname: Hu
authors.affiliation: Department of Molecular Biology and Biochemistry, University of California, Irvine, Irvine, CA, 92697-3900, USA.|Department of Chemistry, University of California, Irvine, Irvine, CA, 92697-2025, USA.
authors.forename: Markus W
authors.initials: MW
authors.lastname: Ribbe
mesh_terms: D001419:Bacteria / Q000737:chemistry / Q000201:enzymology*; D040761:Biomimetic Materials / Q000138:chemical synthesis / Q000737:chemistry*; D032701:Biomimetics; D002245:Carbon Dioxide / Q000737:chemistry; D002248:Carbon Monoxide / Q000737:chemistry; D003067:Coenzymes / Q000138:chemical synthesis / Q000737:chemistry*; D008958:Models, Molecular; D008982:Molybdenum / Q000737:chemistry*; D008983:Molybdoferredoxin / Q000138:chemical synthesis / Q000737:chemistry*; D009591:Nitrogenase / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction
chemical_list: D003067:Coenzymes; D008983:Molybdoferredoxin; D002245:Carbon Dioxide; D002248:Carbon Monoxide; D008982:Molybdenum; D009591:Nitrogenase
keywords: CO/CO2 reduction; cofactors; hydrocarbons; molybdenum; nitrogenases