Details

Autor(en) / Beteiligte

• Nguyen, Trong-Nghia
• Putikam, Raghunath
• Lin, M C

Titel

A novel and facile decay path of Criegee intermediates by intramolecular insertion reactions via roaming transition states

Ist Teil von

• The Journal of chemical physics, 2015-03, Vol.142 (12), p.124312-124312

Ort / Verlag

United States: American Institute of Physics

Erscheinungsjahr

2015

Quelle

AIP Journals

Beschreibungen/Notizen

• 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.