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- W1989741567 abstract "From a combination of isotopic substitution, time-resolved measurements and sequential collision experiments, it was proposed that whereas ionized methyl acetate prior to fragmentation rearranges largely into documentclass{article}pagestyle{empty}begin{document}$ {rm CH}_3 mathop {rm C}limits^ + ({rm OH}){rm O}mathop {rm C}limits^{rm .} {rm H}_2 $end{document}, in contrast, methyl propanoate molecular ions isomerize into documentclass{article}pagestyle{empty}begin{document}$ mathop {rm C}limits^. {rm H}_2 {rm CH}_2 mathop {rm C}limits^ + ({rm OH}){rm OCH}_3 $end{document}. Metastably fragmenting methyl acetate molecular ions are known predominantly to form H2ĊOH together with documentclass{article}pagestyle{empty}begin{document}$ {rm CH}_3 - mathop {rm C}limits^ + = {rm O} $end{document}, whereas ionized methyl propanoate largely yields H3CO˙ together with documentclass{article}pagestyle{empty}begin{document}$ {rm CH}_3 {rm CH}_2 - mathop {rm C}limits^ + = {rm O} $end{document}. The observations were explained in terms of the participation of different distonic molecular ions. The enol form of ionized methyl acetate generates substantially more H3CO˙ in admixture with H2ĊOH than the keto tautomer. This is ascribed to the rearrangement of the enol ion to the keto form being partially rate determining, which results in a wider range of internal energies among metastably fragmenting enol ions. Extensive ab initio calculations at a high level of theory would be required to establish detailed reaction mechanisms." @default.
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- W1989741567 date "1986-09-01" @default.
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- W1989741567 title "Gas phase ion chemistry of methyl acetate, methyl propanoate and their enolic tautomers. An experimental approach" @default.
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- W1989741567 doi "https://doi.org/10.1002/oms.1210210905" @default.
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