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Oxidation of Aryl Diphenylmethyl Sulfides Promoted by a Nonheme Iron(IV)-Oxo Complex: Evidence for an Electron Transfer-Oxygen Transfer Mechanism

Oxidation of Aryl Diphenylmethyl Sulfides Promoted by a Nonheme Iron(IV)-Oxo Complex: Evidence for an Electron Transfer-Oxygen Transfer Mechanism

Journal of Organic Chemistry 81(6): 2513-2520

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)Fe(IV)═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(-)).

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Accession: 058488229

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PMID: 26886491

DOI: 10.1021/acs.joc.6b00099

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