Abstract
We report room-temperature cavity ring-down (CRD) spectra of the à ← X̃ electronic transition of 1-, 2-, and 3-methylallyl peroxy (MAOO•) radicals produced by 193 nm photolysis of methyl-substituted allyl chlorides in the presence of O2. Vibronic structure of experimentally observed spectra was simulated using calculated relative populations of MAOO• conformers, their electronic transition frequencies and oscillator strengths, as well as their vibrational frequencies and Franck-Condon factors of the à ← X̃ electronic transition. The reaction intermediate for the production of 1- and 3-MAOO• radicals, CH3CHCHCH2, is a resonance-stabilized free radical. CRD spectra of 1- and 3-MAOO• radicals obtained using different precursors suggest that allylic rearrangement between the two resonance structures (CH3CH=CHCH2• and CH3CH•CH=CH2) is significantly faster than oxygen addition. Branching ratio between terminal and nonterminal oxygen addition was predicted to be 52:48 on the basis of calculated spin densities, which agrees qualitatively with the experimental CRD spectra of 1- and 3-MAOO• radicals.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
