H-shift and cyclization reactions in unsaturated alkylperoxy radicals near room temperature: propagating or terminating autoxidation?

ABSTRACT: The autoxidation of alkylperoxy radicals (RO₂, where R is organic) is an important degradation pathway for organic compounds in a wide range of chemical systems including Earth's atmosphere. It is thought to proceed by internal H-shift reactions and, for unsaturated radicals, cyclization. However, experimental data on specific reactions steps for unsaturated RO₂ is scarce. This work investigates the unimolecular reactions of 1-butenyl-O₂, 1-pentenyl-O₂, 1-hexenyl-O₂, and 2-methyl-2-pentenyl-O₂ radicals near room temperature (302 ± 3 K) experimentally, by monitoring the radicals directly, and theoretically. The experimental rate coefficients are in good agreement with those determined with high-level quantum calculations, con

SUBMITTER: Noziere B 

PROVIDER: S-EPMC11418804 | biostudies-literature | 2024 Oct

REPOSITORIES: biostudies-literature