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
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- 作者：Alessia Barbieri ; Tiziana Del Giacco ; Stefano Di StefanoOsvaldo Lanzalunga ; Andrea LapiMarco Mazzonna ; Giorgio Olivo
- 刊名：Journal of Organic Chemistry
- 出版年：2016
- 出版时间：December 16, 2016
- 年：2016
- 卷：81
- 期：24
- 页码：12382-12387
- 全文大小：439K
- ISSN：1520-6904
文摘
The oxidation of aryl 1-methyl-1-phenylethyl sulfides promoted by the nonheme iron(IV)–oxo complexes [(N4Py)Fep>IV p>═O]p>2+ p> and [(Bn-TPEN)Fep>IV p>═O]p>2+ p> occurs by an electron transfer–oxygen rebound (ET–OT) mechanism leading to aryl 1-methyl-1-phenylethyl sulfoxides accompanied by products derived 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 in the range of <0.8 × 10p>4 p> to 3.5 × 10p>4 p> sp>–1 p>, were determined from the fragmentation rate constants of the radical cations (kf) and the S oxidation/fragmentation product ratios.