The new binuclear oxothiolatorhenium(V) compound, Re 2 O 2 (mtp) 3 ( D 1, mtpH 2 = 2-mercaptomethylthiophenol) was found to be an efficient catalyst for oxygen-transfer reactions. Strong Lewis bases such as phosphines coordinate to one of the rhenium centers in D 1; we suggest that this opens one of the Re−S bridges. Dialkylsulfides coordinate weakly to D 1 . Alkylarylsulfides, diarylsulfides, triphenylarsine and triphenylstibine, and dienes and alkenes do not coordinate to D 1 . D 1 catalyzes the oxidation of phosphines, arsines, stibenes, sulfides, and dienes by pyridine N -oxides and catalyzes the oxidation of phosphines by dimethyl sulfoxide. The kinetics and mechanism for the oxidation of triarylphosphines by pyridine N -oxides were investigated. The relative reactivities of all substrates were studied by competitive reactions. The order was found to be phosphine > arsine > stibene > sulfide > diene. The reaction is proposed to go through a Re(VII) intermediate with pyridine N -oxide as one of the ligands. The N−O bond was activated through coordination to rhenium, and the oxygen atom was abstracted by a phosphine forming a phosphine oxide.
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Huang et al. (2001) studied this question.
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