Photodeoxygenation of Dibenzothiophene Sulfoxide: Evidence for a Unimolecular S-O Cleavage Mechanism1

Photolysis of dibenzothiophene sulfoxide results in the formation of dibenzothiophene and oxidized solvent. Though quantum yields are low, chemical yields of the sulfide are quite high. Yields of the oxidized solvents can also be high. Typical products are phenol from benzene, cyclohexanol, and cyclohexene from cyclohexane and 2-cyclohexenol and epoxycyclohexane from cyclohexene. A number of experiments designed to elucidate the mechanism of the hydroxylation were carried out, including measurements of quantum yields as a function of concentration, solvent, quenchers, and excitation wavelength. These data are inconsistent with a mechanism involving a sulfoxide dimer, which also does not properly account for the solvent oxidations. It is suggested that the active oxidizing agent may be atomic oxygen O(3P) or a closely related noncovalent complex, based on the nature of the oxidation chemistry, comparison to known rate constants for O(3P) reactivity, and the quantum yield data.