文摘
The oxidation of a series of aryl diphenylmethyl sulfides (4-X-C6H4SCH(C6H5)2, where X = OCH3 (1), X = CH3 (2), X = H (3), and X = CF3 (4)) promoted by the nonheme iron(IV)-oxo complex [(N4Py)FeIV═O]2+ occurs by an electron transfer-oxygen transfer (ET-OT) mechanism as supported by the observation of products (diphenylmethanol, benzophenone, and diaryl disulfides) deriving from α-C–S and α-C–H fragmentation of radical cations 1+•–4+•, formed besides the S-oxidation products (aryl diphenylmethyl sulfoxides). The fragmentation/S-oxidation product ratios regularly increase through a decrease in the electron-donating power of the aryl substituents, that is, by increasing the fragmentation rate constants of the radical cations as indicated by a laser flash photolysis (LFP) study of the photochemical oxidation of 1–4 carried out in the presence of N-methoxyphenanthridinium hexafluorophosphate (MeOP+PF6–).