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投稿者: Yuma Morimoto
Nonheme Iron Mediated Oxidation of Light Alkanes with Oxone: Characterization of Reactive Oxoiron(IV) Ligand Cation Radical Intermediates by Spectroscopic Studies and DFT Calculations
Angewandte Chemie International Edition by Chun-Wai Tse, Toby Wai-Shan Chow, Zhen Guo, Hung Kay Lee, Jie-Sheng Huang, Chi-Ming Che  /  21d  //  keep unread  //  hide  //  preview

Abstract

The oxidation of light alkanes that is catalyzed by heme and nonheme iron enzymes is widely proposed to involve highly reactive {FeVO} species or {FeIVO} ligand cation radicals. The identification of these high-valent iron species and the development of an iron-catalyzed oxidation of light alkanes under mild conditions are of vital importance. Herein, a combination of tridentate and bidentate ligands was used for the generation of highly reactive nonheme {FeO} species. A method that employs [FeIII(Me3tacn)(Cl-acac)Cl]+ as a catalyst in the presence of oxone was developed for the oxidation of hydrocarbons, including cyclohexane, propane, and ethane (Me3tacn=1,4,7-trimethyl-1,4,7-triazacyclononane; Cl-acac=3-chloro-acetylacetonate). The complex [FeIII(Tp)2]+ and oxone enabled stoichiometric oxidation of propane and ethane. ESI-MS, EPR and UV/Vis spectroscopy, 18O labeling experiments, and DFT studies point to [FeIV(Me3tacn)({Cl-acac}.+)(O)]2+ as the catalytically active species.
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Highly reactive {FeO} intermediates, such as [Fe(Tp)2(O)]+ or complex I (see Scheme), are likely to be involved in the oxidation of propane and ethane with oxone that is either mediated by [FeIII(Tp)2]+ (1) or catalyzed by iron complex 2. The cationic intermediate Ifeatures an {FeO} moiety and is stabilized by a combination of tridentate and bidentate ligands.
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