標題: | A novel and facile decay path of Criegee intermediates by intramolecular insertion reactions via roaming transition states |
作者: | Trong-Nghia Nguyen Putikam, Raghunath Lin, M. C. 應用化學系 應用化學系分子科學碩博班 Department of Applied Chemistry Institute of Molecular science |
公開日期: | 28-三月-2015 |
摘要: | We have discovered a new and highly competitive product channel in the unimolecular decay process for small Criegee intermediates, CH2OO and anti/syn-CH3C(H)OO, occurring by intramolecular insertion reactions via a roaming-like transition state (TS) based on quantum-chemical calculations. Our results show that in the decomposition of CH2OO and anti-CH3C(H)OO, the predominant paths directly produce cis-HC(O)OH and syn-CH3C(O)OH acids with >110 kcal/mol exothermicities via loose roaming-like insertion TSs involving the terminal O atom and the neighboring C-H bonds. For syn-CH3C(H)OO, the major decomposition channel occurs by abstraction of a H atom from the CH3 group by the terminal O atom producing CH2C(H)O-OH. At 298 K, the intramolecular insertion process in CH2OO was found to be 600 times faster than the commonly assumed ring-closing reaction. (c) 2015 AIP Publishing LLC. |
URI: | http://dx.doi.org/10.1063/1.4914987 http://hdl.handle.net/11536/124709 |
ISSN: | 0021-9606 |
DOI: | 10.1063/1.4914987 |
期刊: | JOURNAL OF CHEMICAL PHYSICS |
Volume: | 142 |
Issue: | 12 |
顯示於類別: | 期刊論文 |