Title: A novel and facile decay path of Criegee intermediates by intramolecular insertion reactions via roaming transition states
Authors: Trong-Nghia Nguyen
Putikam, Raghunath
Lin, M. C.
Department of Applied Chemistry
Institute of Molecular science
Issue Date: 28-Mar-2015
Abstract: 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
ISSN: 0021-9606
DOI: 10.1063/1.4914987
Volume: 142
Issue: 12
Appears in Collections:Articles