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.

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