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.
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.
Sugimoto
Hideki
H
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
Tano
Hiroyuki
H
Toyota
Kazuo
K
Tajima
Reiko
R
Miyake
Hiroyuki
H
Takahashi
Isao
I
Hirota
Shun
S
Itoh
Shinobu
S
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*
D004220:Disulfides; D009942:Organometallic Compounds; D006859:Hydrogen; D010088:Oxidoreductases; D014414:Tungsten