Unusual Diradical Intermediates in Ozonolysis of Alkenes: A Combined Theoretical and Synchrotron Radiation Photoionization Mass Spectrometric Study on Ozonolysis of Alkyl Vinyl Ethers.
J Phys Chem A
; 126(43): 8021-8027, 2022 Nov 03.
Article
en En
| MEDLINE
| ID: mdl-36259764
ABSTRACT
Calculations and experiments were conducted on ozonolysis of ethyl vinyl ether (EVE) and butyl vinyl ether to identify an unconventional diradical intermediate generated from the O-O bond cleavage of primary ozonide. The diradical can undergo a H atom shifting process that yields keto-hydroperoxide (KHP), the characteristic product that identifies the existence of a diradical intermediate. RRKM-ME calculation, based on the PES at the CCSD(T)/VTZ//M06-2X/6-311++G(2df,2p) level, disclosed branching ratios of â¼0.65% for KHP formation. Using synchrotron-generated vacuum-ultraviolet photoionization mass spectrometry measurements, the formation of KHPs (C4H8O4) in ozonolysis of EVE was confirmed by ion signals of C4H8O4+ (ionization of KHP) and C4H7O2+ (ion fragment from the loss of HO2 from KHP) by comparing their photoionization efficiency spectra with the calculated adiabatic ionization energies and appearance energies.
Texto completo:
1
Colección:
01-internacional
Base de datos:
MEDLINE
Tipo de estudio:
Prognostic_studies
Idioma:
En
Revista:
J Phys Chem A
Asunto de la revista:
QUIMICA
Año:
2022
Tipo del documento:
Article
País de afiliación:
China