title: A nitrogenase cluster model [Fe8S6O] with an oxygen unsymmetrically bridging two proto-Fe4S3 cubes: relevancy to the substrate binding mode of the FeMo cofactor.
abstract: An oxygen-encapsulated iron sulfido cluster, [(DmpS)Fe(4)S(3)O][(DmpS)Fe(4)S(3)](μ-SDmp)(2)(μ-OCPh(3)) (2; Dmp = 2,6-(mesityl)(2)C(6)H(3)), has been synthesized by the reaction of the preformed dinuclear iron thiolate/alkoxide [(Ph(3)CO)Fe](2)(μ-SDmp)(2) (1) with (1/8)S(8) and (1/4)H(2)O in toluene. In the [Fe(8)S(6)O] core, the oxygen atom bridges unsymmetrically two incomplete Fe(4)S(3) cubes, and two coordinatively unsaturated iron atoms are weakly bound to mesityl rings. Relevance of the cluster structure of 2 to the nitrogenase FeMo cofactor and its substrate binding mode is discussed.
authors.affiliation: Department of Chemistry, Graduate School of Science, and Research Center for Meterials Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan.
authors.forename: Shun
authors.initials: S
authors.lastname: Ohta
authors.forename: Yasuhiro
authors.initials: Y
authors.lastname: Ohki
authors.forename: Takayoshi
authors.initials: T
authors.lastname: Hashimoto
authors.forename: Roger E
authors.initials: RE
authors.lastname: Cramer
authors.forename: Kazuyuki
authors.initials: K
authors.lastname: Tatsumi
mesh_terms: D058085:Iron Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D008958:Models, Molecular; D008983:Molybdoferredoxin / Q000737:chemistry* / Q000378:metabolism; D010100:Oxygen / Q000737:chemistry*; D011485:Protein Binding; D013440:Sulfides / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D058085:Iron Compounds; D008983:Molybdoferredoxin; D013440:Sulfides; D010100:Oxygen