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• W2110331231 endingPage "10473" @default.
• W2110331231 startingPage "10467" @default.
• W2110331231 abstract "Activation barriers (ΔHMe⧧) for adding methyl radicals to ions of the general formula CH3CROCH3+ have been measured by looking at the threshold energies for the reverse reaction, dissociative photoionization of ethers of the general formula RC(CH3)2OCH3. Dissociation by loss of a methyl radical has more favorable thermochemistry than loss of R•, yet the onset of R• loss occurs at lower energies than loss of CH3•. In other words, the more endothermic dissociation exhibits a lower appearance energy. Contrathermodynamic ordering of appearance energies is observed for R = Et, nPr, iPr, tBu, and neopentyl. The sum of the appearance energy difference, ΔAE, and the thermochemical difference (ΔΔH, calculated using G3 theory) gives a lower bound for the barrier for adding methyl radical to CH3CROCH3+. More specifically, the difference between that activation barrier and the one for adding R• to (CH3)2COCH3+, ΔHMe⧧ − ΔHR⧧, equals ΔAE + ΔΔH and has values in the range 20−24 kJ mol-1 for the homologous series investigated. There is no systematic trend with the steric bulk of R, and available evidence suggests that ΔHR⧧ does not have a value >5 kJ mol-1. The difference in barrier heights, ΔHMe⧧ − ΔHiPr⧧ for CH3• plus iPrC(CH3)OX+ vs iPr• + (CH3)2COX+, has the same value, regardless of whether X = H or CH3. Mixing of higher energy electronic configurations provides a qualitative theoretical explanation for some (but not all) observed trends in barrier heights." @default.
• W2110331231 created "2016-06-24" @default.
• W2110331231 creator A5021559669 @default.
• W2110331231 creator A5029058810 @default.
• W2110331231 date "2005-10-22" @default.
• W2110331231 modified "2023-10-16" @default.
• W2110331231 title "Activation Barriers for Addition of Methyl Radicals to Oxygen-Stabilized Carbocations" @default.
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• W2110331231 doi "https://doi.org/10.1021/jp052790a" @default.
• W2110331231 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/16833345" @default.
• W2110331231 hasPublicationYear "2005" @default.
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