Unimolecular Reactions of 2,4-Dimethyloxetanyl Radicals.

ABSTRACT: Alkyl-substituted oxetanes are cyclic ethers formed via unimolecular reactions of QOOH radicals produced via a six-membered transition state in the preceding isomerization step of organic peroxy radicals, ROO. Owing to radical isomer-specific formation pathways, cyclic ethers are unambiguous proxies for inferring QOOH reaction rates. Therefore, accounting for subsequent oxidation of cyclic ethers is important in order to accurately determine rates for QOOH → products. Cyclic ethers can react via unimolecular reaction (ring-opening) or via bimolecular reaction with O₂ to form cyclic ether-peroxy adducts. The computations herein provide reaction mechanisms and theoretical rate coefficients for the former type in order to determine competing pathways for the cyclic ether radicals.

SUBMITTER: Doner AC 

PROVIDER: S-EPMC10041641 | biostudies-literature | 2023 Mar

REPOSITORIES: biostudies-literature