Arylruthenium(III) Porphyrin-Catalyzed C-H Oxidation and Epoxidation at Room Temperature and [RuV(Por)(O)(Ph)] Intermediate by Spectroscopic Analysis and Density Functional Theory Calculations.
The development of highly active and selective metal catalysts for efficient oxidation of hydrocarbons and identification of the reactive intermediates in the oxidation catalysis are long-standing challenges. In the rapid hydrocarbon oxidation catalyzed by ruthenium(IV) and -(III) porphyrins, the pu...
| Publicado en: | Journal of the American Chemical Society Vol. 140; no. 22; pp. 7032 - 7043 |
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| Autores principales: | , , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
6/6/2018
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=130028719&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 130028719 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 6/6/2018 vid: 140 iid: 22 pid: 997 pub: American Chemical Society artinfo: ui: 130028719 10.1021/jacs.8b04470 ppf: 7032 ppct: 11 formats: tig: atl: Arylruthenium(III) Porphyrin-Catalyzed C-H Oxidation and Epoxidation at Room Temperature and [RuV(Por)(O)(Ph)] Intermediate by Spectroscopic Analysis and Density Functional Theory Calculations. aug: au: Shing, Ka-Pan Cao, Bei Liu, Yungen Li, Ming-De Phillips, David Lee Chang, Xiao-Yong Che, Chi-Ming Lee, Hung Kay affil: Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China[sup HKU Shenzhen Institute of Research and Innovation, Shenzhen 518053, China Department of Cell Biology, New York University Medical Center, New York, New York, U.S.A su: Oxidation Epoxidation Spectroscopic imaging Density functional theory Metal catalysts sug: subj: Oxidation Epoxidation Spectroscopic imaging Density functional theory Metal catalysts ab: The development of highly active and selective metal catalysts for efficient oxidation of hydrocarbons and identification of the reactive intermediates in the oxidation catalysis are long-standing challenges. In the rapid hydrocarbon oxidation catalyzed by ruthenium(IV) and -(III) porphyrins, the putative Ru(V)-oxo intermediates remain elusive. Herein we report that arylruthenium(III) porphyrins are highly active catalysts for hydrocarbon oxidation. Using catalyst [Ru(TDCPP)(Ph)(OEt)] (HTDCPP = 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin), the oxidation of C-H bonds of various hydrocarbons with oxidant m-CPBA at room temperature gave alcohols/ketones in up to 99% yield within 1 h; use of [BuN]IO as a mild alternative oxidant avoided formation of lactone from cyclic ketone in C-H oxidation, and the catalytic epoxidation with up to 99% yield and high selectivity (no aldehydes as side product) was accomplished within 5 min. UV-vis, electrospray ionization-mass spectrometry, resonance Raman, electron paramagnetic resonance, and kinetic measurements and density functional theory calculations lend evidence for the formation of Ru(V)-oxo intermediate [Ru(TDCPP)(O)(Ph)]. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2018 holdings: @attributes: islocal: N |
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