Abstract
The probable fragmentation channels of hydroxymethyl radical cation were studied through the Hand H2-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 H2. The fragmentation reaction to form CHO + and H2 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 2OH+ is more difficult than that from the methylene group. The feasible path to lose H is to generate CHOH2+ 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 CH2+ 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.
| Original language | English |
|---|---|
| Pages (from-to) | 285-292 |
| Number of pages | 8 |
| Journal | Journal of the Chinese Chemical Society |
| Volume | 54 |
| Issue number | 2 |
| Publication status | Published - 2007 |
| Externally published | Yes |
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Keywords
- Conformation
- Fragmentation
- Hydroxymethyl cation
ASJC Scopus subject areas
- Chemistry(all)
Cite this
Fragmentations of hydroxymethyl radical cation : An ab initio study. / Mai, Fu D.; Lu, Hsiu Feng; Li, Feng Y.; Lin, Sheng Hsien.
In: Journal of the Chinese Chemical Society, Vol. 54, No. 2, 2007, p. 285-292.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Fragmentations of hydroxymethyl radical cation
T2 - An ab initio study
AU - Mai, Fu D.
AU - Lu, Hsiu Feng
AU - Li, Feng Y.
AU - Lin, Sheng Hsien
PY - 2007
Y1 - 2007
N2 - The probable fragmentation channels of hydroxymethyl radical cation were studied through the Hand H2-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 H2. The fragmentation reaction to form CHO + and H2 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 2OH+ is more difficult than that from the methylene group. The feasible path to lose H is to generate CHOH2+ 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 CH2+ 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.
AB - The probable fragmentation channels of hydroxymethyl radical cation were studied through the Hand H2-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 H2. The fragmentation reaction to form CHO + and H2 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 2OH+ is more difficult than that from the methylene group. The feasible path to lose H is to generate CHOH2+ 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 CH2+ 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.
KW - Conformation
KW - Fragmentation
KW - Hydroxymethyl cation
UR - http://www.scopus.com/inward/record.url?scp=34548657899&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=34548657899&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:34548657899
VL - 54
SP - 285
EP - 292
JO - Journal of the Chinese Chemical Society
JF - Journal of the Chinese Chemical Society
SN - 0009-4536
IS - 2
ER -