title: Reduction of bis(dithiolene)oxo(disulfido)tungsten(VI) complex with dihydrogen related to the chemical function of the fourth tungsten-containing enzyme (WOR4) from Pyrococcus furiosus.
abstract: Sulfurization of five-coordinate [W(IV)O(1,2-benzenedithiolate)(2)](2-) proceeds under very mild conditions to form seven-coordinate [W(VI)O(eta(2)-S(2))(1,2-benzenedithiolate)(2)](2-), from which H(2)S was generated by treatment with H(2). This is the first functional model for the fourth tungsten-containing WOR4 enzyme. Kinetics and isotope-scrambling experiments have suggested the existence of six-coordinate W(V)(eta(1)-S(2)) species as a key reaction intermediate.
authors.affiliation: Department of Material and Life Science, Division of Advanced Science and Biotechnology, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan. sugimoto@mls.eng.osaka-u.ac.jp
authors.forename: Hideki
authors.initials: H
authors.lastname: Sugimoto
authors.forename: Hiroyuki
authors.initials: H
authors.lastname: Tano
authors.forename: Kazuo
authors.initials: K
authors.lastname: Toyota
authors.forename: Reiko
authors.initials: R
authors.lastname: Tajima
authors.forename: Hiroyuki
authors.initials: H
authors.lastname: Miyake
authors.forename: Isao
authors.initials: I
authors.lastname: Takahashi
authors.forename: Shun
authors.initials: S
authors.lastname: Hirota
authors.forename: Shinobu
authors.initials: S
authors.lastname: Itoh
mesh_terms: D004220:Disulfides / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry* / Q000378:metabolism; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry* / Q000378:metabolism*; D010084:Oxidation-Reduction; D010088:Oxidoreductases / Q000737:chemistry / Q000378:metabolism*; D020027:Pyrococcus furiosus / Q000201:enzymology*; D014414:Tungsten / Q000737:chemistry*
chemical_list: D004220:Disulfides; D009942:Organometallic Compounds; D006859:Hydrogen; D010088:Oxidoreductases; D014414:Tungsten