%0 Journal Article %A Zargari, Nima %A Winter, Pierre %A Liang, Yong %A Lee, Joo Ho %A Cooksy, Andrew %A Houk, K. N. %A Jung, Kyung Woon %D 2016 %T Unexpected, Latent Radical Reaction of Methane Propagated by Trifluoromethyl Radicals %U https://acs.figshare.com/articles/journal_contribution/Unexpected_Latent_Radical_Reaction_of_Methane_Propagated_by_Trifluoromethyl_Radicals/4003512 %R 10.1021/acs.joc.6b01903.s001 %2 https://acs.figshare.com/ndownloader/files/6417750 %K hydrogen peroxide %K reaction cycle %K Latent Radical Reaction %K carbonyl carbon %K methane gas %K metal-catalyzed oxidation reactions %K TFAA %K Computational studies %K DFT calculations %K CF %K methyl carbon %K acetic acid %K Trifluoromethyl Radicals Thorough %K Methane Propagated %X 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 (•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. %I ACS Publications