Selectivity in the TiO2-mediated photocatalytic oxidation of thioethers

Article abstract of DOI:10.1016/S0040-4039(00)97667-6

The relative rates of photooxygenation of substituted diphenyl sulfides on irradiated TiO₂ powders suspended in oxygenated acetonitrile correlate linearly with σ⁺, as is consistent with formation of a surface bound cation radical in the primary photoprocess. Substituted dibenzyl sulfides, in contrast, suffer C-S cleavage upon photocatalyzed oxidation. Factors disposing these reactions toward preferential sulfoxide formation or bond cleavage are discussed.