期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 81, 期 20, 页码 9820-9825出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.joc.6b01903
关键词
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资金
- Hydrocarbon Research Foundation
- NIH [S10 RR025432]
- NSF [CHE-1361104]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1361104] Funding Source: National Science Foundation
Thorough mechanistic studies and DFT calculations revealed a background radical pathway latent in metal-catalyzed oxidation reactions of methane at low temperatures. Use of hydrogen peroxide with TFAA generated a trifluoromethyl radical (center dot CF3), which in turn reacted with methane gas to selectively yield acetic acid. It was found that the methyl carbon of the product was derived from methane, while the carbonyl carbon was derived from TFAA. Computational studies also support these findings, revealing the reaction cycle to be energetically favorable.
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