Nonheme Iron Mediated Oxidation of Light Alkanes with Oxone: Characterization of Reactive Oxoiron(IV) Ligand Cation Radical Intermediates by Spectroscopic Studies and DFT Calculations |
| |
| Authors: | Chun‐Wai Tse Dr. Toby Wai‐Shan Chow Dr. Zhen Guo Prof. Dr. Hung Kay Lee Dr. Jie‐Sheng Huang Prof. Dr. Chi‐Ming Che |
| |
| Affiliation: | 1. State Key Laboratory of Synthetic Chemistry, Institute of Molecular Functional Materials and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong (China);2. Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong (China);3. HKU Shenzhen Institute of Research and Innovation, Shenzhen 518053 (China) |
| |
| Abstract: | The oxidation of light alkanes that is catalyzed by heme and nonheme iron enzymes is widely proposed to involve highly reactive {FeV?O} species or {FeIV?O} 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 {Fe?O} 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. |
| |
| Keywords: | alkanes iron nonheme iron complexes oxidation oxoiron complexes |
|
|
