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DOI: 10.1039/A601264G (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1997, 391-396

The expulsion of alkyl radicals from the methyliumylaminomethyl radical cation, ˙CH2NH2CH3+, and related distonic ions

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Steen Hammerum, Allan C. Petersen, Theis I. Sølling, Tore Vulpius and Herman Zappey

Abstract

The dissociation of metastable ˙CH2NH2CH3+ ions into CH3˙ and CH2[double bond, length as m-dash]NH2+ is accompanied by a remarkably high translational energy release, demonstrating that the addition of a methyl radical to the N-terminus of CH2[double bond, length as m-dash]NH2+ has an appreciable energy barrier. Isotope labelling shows the reaction to be highly specific. Alkyl radical loss from a number of substituted α-distonic ions was also examined; the kinetic energy release accompanying loss of ethyl radicals from N-ethyl α-distonic ions, CH3CH2N+H2ĊHR, varies with the nature of R. The energy barrier for dissociation and the relative energies of the five C2H7N˙+ isomers was examined with the G2(MP2) and CBS-Q composite theoretical methods.

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