jo6b01903_si_001.pdf (2.67 MB)
Unexpected, Latent Radical Reaction of Methane Propagated by Trifluoromethyl Radicals
journal contribution
posted on 2016-09-29, 00:00 authored by Nima Zargari, Pierre Winter, Yong Liang, Joo Ho Lee, Andrew Cooksy, K. N. Houk, Kyung Woon JungThorough
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 (•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.