The oxidation of aryl 1-methyl-1-phenylethyl sulfides promoted by the nonhemeiron(IV) oxo complexes [(N4Py)FeIV=O]2+ and [(Bn-TPEN)FeIV=O]2+ occurs by an electrotransfer - oxygen rebound (ET-OT) mechanism leading to aryl 1-methyl-1-phenylethyl sulfoxides accompanied by products deriving from Cα-S fragmentation of sulfide radical cations (2-phenyl-2- propanol and diaryl disulfides). For the first time the rate constants for the oxygen rebound process (kOT), which are comprised in the range <0.8×104 s-1 - 3.5×104 s-1, were determined from the fragmentation rate constants of the radical cations (kf) and the S-oxidation/fragmentation product ratios. ratios.
Electron Transfer Mechanism in the Oxidation of Aryl 1-Methyl-1-phenylethyl Sulfides Promoted by Nonheme Iron(IV)-Oxo Complexes: The Rate of the Oxygen Rebound Process
DEL GIACCO, Tiziana;
2016
Abstract
The oxidation of aryl 1-methyl-1-phenylethyl sulfides promoted by the nonhemeiron(IV) oxo complexes [(N4Py)FeIV=O]2+ and [(Bn-TPEN)FeIV=O]2+ occurs by an electrotransfer - oxygen rebound (ET-OT) mechanism leading to aryl 1-methyl-1-phenylethyl sulfoxides accompanied by products deriving from Cα-S fragmentation of sulfide radical cations (2-phenyl-2- propanol and diaryl disulfides). For the first time the rate constants for the oxygen rebound process (kOT), which are comprised in the range <0.8×104 s-1 - 3.5×104 s-1, were determined from the fragmentation rate constants of the radical cations (kf) and the S-oxidation/fragmentation product ratios. ratios.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
