Article
2025
·
0 citations
Revisiting Reaction Mechanism of Regioselective Disulfide-Catalyzed Photocatalytic Aerobic Oxidative Cleavage of 1-Arylbutadienes: A Computational Study
Abstract
A computational study of the regioselective aerobic oxidative cleavage of 1-arylbutadienes is carried out employing density functional theory and high-level coupled-cluster methods, such as coupled-cluster singles and doubles with perturbative triples [CCSD(T)]. The results demonstrate that the reaction proceeds either via the intramolecular reduction or dimerization of peroxyl radical. These findings are in contrast to a previously proposed mechanism that progresses via formation of the dioxetane ring. The computations further indicate that the homolysis of S-S bond of diaryl disulfide derivatives cannot be achieved by irradiation with direct visible light under the reaction conditions due to the high bond dissociation energy.
Keywords
aerobic oxidative cleavage
arylbutadienes
density functional theory
diaryl disulfides
DLPNO-CCSD(T)
GAUSSIAN-BASIS SETS
CORRELATED MOLECULAR CALCULATIONS
C DOUBLE-BOND
PHOTOOXIDATIVE CLEAVAGE
METAL-FREE
ALKENES
OXYGEN
ABSORPTION
SULFOXIDES
RADICALS
WoS Categories
Chemistry, Physical
Physics, Atomic, Molecular & Chemical
Citation
- Journal
- CHEMPHYSCHEM
- Year
- 2025
- Volume
- 26
- Issue
- 11
- ISSN
- 1439-4235
- eISSN
- 1439-7641
- DOI
- 10.1002/cphc.202401004
- WoS UID
- WOS:001465959300001