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(-)).

Barbieri, A., De Carlo Chimienti, R., Del Giacco, T., Di Stefano, S., Lanzalunga, O., Lapi, A., et al. (2016). 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 [10.1021/acs.joc.6b00099].

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

SALAMONE, MICHELA
2016

Abstract

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(-)).
Pubblicato
Rilevanza internazionale
Articolo
Esperti anonimi
Settore CHIM/06 - Chimica Organica
English
Con Impact Factor ISI
Barbieri, A., De Carlo Chimienti, R., Del Giacco, T., Di Stefano, S., Lanzalunga, O., Lapi, A., et al. (2016). 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 [10.1021/acs.joc.6b00099].
Barbieri, A; De Carlo Chimienti, R; Del Giacco, T; Di Stefano, S; Lanzalunga, O; Lapi, A; Mazzonna, M; Olivo, G; Salamone, M
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2108/172201
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