Photosensitized oxidation of sulfides: discriminating between the singlet-oxygen mechanism and electron transfer involving superoxide anion or molecular oxygen

The oxidation of diethyl and diphenyl sulfide photosensitized by dicyanoanthracene (DCA), N-methylquinolinium tetrafluoroborate (NMQ(+)), and triphenylpyrylium tetrafluoroborate (TPP(+)) has been explored by steady-state and laser flash photolysis studies in acetonitrile, methanol, and 1,2-dichloroethane. In the Et(2)S/DCA system sulfide-enhanced intersystem crossing leads to generation of (1)O(2), which eventually gives the sulfoxide via a persulfoxide; this mechanism plays no role with Ph(2)S, though enhanced formation of (3)DCA has been demonstrated. In all other cases an electron-transfer (ET) mechanism is involved. Electron-transfer sulfoxidation occurs with efficiency essentially independent of the sulfide structure, is subject to quenching by benzoquinone, and does not lead to Ph(2)SO cooxidation. Formation of the radical cations R(2)S(*+) has been assessed by flash photolysis (medium-dependent yield, dichloroethane>CH(3)CN>CH(3)OH) and confirmed by quenching with 1,4-dimethoxybenzene. Electron-transfer oxidations occur both when the superoxide anion is generated by the reduced sensitizer (DCA(*-), NMQ(*)) and when this is not the case (TPP(*)). Although it is possible that different mechanisms operate with different ET sensitizers, a plausible unitary mechanism can be proposed. This considers that reaction between R(2)S(*+) and O(2)(*-) mainly involves back electron transfer, whereas sulfoxidation results primarily from the reaction of the sulfide radical cation with molecular oxygen. Calculations indeed show that the initially formed fleeting complex RS(2)(+)...O-O(*) adds to a sulfide molecule and gives strongly stabilized R(2)S-O(*)-(+)O-SR(2) via an accessible transition state. This intermediate gives the sulfoxide, probably via a radical cation chain path. This mechanism explains the larger scope of ET sulfoxidation with respect to the singlet-oxygen process.