title: Synthesis, Characterization, and Nitrogenase-Relevant Reactions of an Iron Sulfide Complex with a Bridging Hydride.
abstract: The FeMoco of nitrogenase is an iron-sulfur cluster with exceptional bond-reducing abilities. ENDOR studies have suggested that E4, the state that binds and reduces N2, contains bridging hydrides as part of the active-site iron-sulfide cluster. However, there are no examples of any isolable iron-sulfide cluster with a hydride, which would test the feasibility of such a species. Here, we describe a diiron sulfide hydride complex that is prepared using a mild method involving C-S cleavage of added thiolate. Its reactions with nitrogenase substrates show that the hydride can act as a base or nucleophile and that reduction can cause the iron atoms to bind N2. These results add experimental support to hydride-based pathways for nitrogenase.
authors.affiliation: Department of Chemistry, Yale University , New Haven, Connecticut 06520, United States.
authors.forename: Nicholas A
authors.initials: NA
authors.lastname: Arnet
authors.affiliation: Department of Chemistry, University of Rochester , Rochester, New York 14627, United States.
authors.forename: Thomas R
authors.initials: TR
authors.lastname: Dugan
authors.affiliation: Department of Chemistry, Yale University , New Haven, Connecticut 06520, United States.
authors.forename: Fabian S
authors.initials: FS
authors.lastname: Menges
authors.affiliation: Department of Chemistry, Yale University , New Haven, Connecticut 06520, United States.
authors.forename: Brandon Q
authors.initials: BQ
authors.lastname: Mercado
authors.affiliation: Department of Chemistry, University of Rochester , Rochester, New York 14627, United States.
authors.forename: William W
authors.initials: WW
authors.lastname: Brennessel
authors.affiliation: Max-Planck-Institut für Chemische Energiekonversion , Mülheim an der Ruhr, Germany.
authors.forename: Eckhard
authors.initials: E
authors.lastname: Bill
authors.affiliation: Department of Chemistry, Yale University , New Haven, Connecticut 06520, United States.
authors.forename: Mark A
authors.initials: MA
authors.lastname: Johnson
authors.affiliation: Department of Chemistry, Yale University , New Haven, Connecticut 06520, United States.
authors.forename: Patrick L
authors.initials: PL
authors.lastname: Holland
mesh_terms: D005296:Ferrous Compounds / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009591:Nitrogenase / Q000737:chemistry*; D015204:Spectroscopy, Mossbauer
chemical_list: D005296:Ferrous Compounds; D006859:Hydrogen; D009591:Nitrogenase; C022597:ferrous sulfide