Abstract: | Trifluoro-t-butoxy radicals have been generated by reacting fluorine with 2-trifluoromethyl propan-2-ol: Over the temperature range 361-600 K the trifluoro-t-butoxy radical decomposes exclusively by loss of the ? CF3 group reaction (?2)] rather than by loss of ? CH3 group reaction (?1)]: The limits of detectability of the product CF3COCH3, by gas-chromatographic analysis, place a lower limit on the ratio k?2/k?1 of ca. 75. The implications of these results in relation to the reverse radical addition reactions to the carbonyl group are discussed along with the thermochemistry of the reactions. |