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Fragmentations of Hydroxymethyl Radical Cation: An Ab Initio Study
Author(s) -
Mai FuDer,
Lu HsiuFeng,
Li FengYin,
Lin ShengHsien
Publication year - 2007
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.200700042
Subject(s) - chemistry , hydroxymethyl , fragmentation (computing) , isomerization , methylene , ab initio , computational chemistry , hydrogen atom abstraction , photochemistry , medicinal chemistry , stereochemistry , hydrogen , organic chemistry , catalysis , computer science , operating system
The probable fragmentation channels of hydroxymethyl radical cation were studied through the H‐and H 2 ‐abstraction and C‐O bond breaking reactions including their related isomerization reactions. The energy barriers for hydroxymethyl cation undergoing isomerization reactions are generally higher than those undergoing the concerted 1,2‐elimination reactions to generate CHO + and H 2 . The fragmentation reaction to form CHO + and H 2 through the 1,2‐elimination pathways is the major fragmentation channel for hydroxymethyl cation, consistent with the experimental observation. H abstraction from the hydroxyl group of CH 2 OH + is more difficult than that from the methylene group. The feasible path to lose H is to generate CHOH 2 + through hydrogen transfer reaction as the first step and then to undergo H‐elimination to generate trans ‐CHOH + . Among all the reactions found in this study, the OH‐elimination to generate CH 2 + has the highest energy barrier. Our calculation results indicate that the major signals contributed from the related species of hydroxymethyl cation found in the mass spectrum should be m/e 29, m/e 30.