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

Sugimoto H; Tano H; Toyota K; Tajima R; Miyake H; Takahashi I; Hirota S; Itoh S

Journal of the American Chemical Society, Vol.132, No.1, 8-8, 2010

Sugimoto H, Tano H, Toyota K, Tajima R, Miyake H, Takahashi I, Hirota S, Itoh S

Sulfurization of five-coordinate [(WO)-O-IV(1,2-benzenedithiolate)2](2-) proceeds under very mild conditions to form seven-coordinate [(WO)-O-VI(eta(2)-S-2)(1,2-benzenedithiolate)(2)](2-), from which H2S 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.