Sulfide oxygenation by tert-butyl hydroperoxide with mononuclear (Me3TACN)Mn catalysts

Mononuclear (Me3TACN)MnX3 compounds, where X is Cl−, Br−, or N3−, and Me3TACN is 1,4,7-N,N′,N″-trimethyl-1,4,7-triazacyclononane, have been tested for catalyzing both sulfide oxygenation and styrene epoxidation by tert-butyl hydroperoxide (TBHP) and display turnover frequencies (TOF) up to 200 h−1 at room temperature. Sulfoxides or sulfones may be produced selectively by varying reaction conditions. Product distribution from the oxygenation reactions of ethyl phenyl sulfide, 2-chloroethyl phenyl sulfide, and styrene is consistent with a mechanism involving an early single-electron transfer (SET) step.