Gas- and liquid-phase ozonolysis of ethylene, butadiene, and perfluoro-olefins: solvation and the cage effect

Quantum-chemical calculations were performed for the primary step of ozonolysis reaction of different olefins: ethylene, 1,3-butadiene, 1,1,2,2-tetrafluoroethylene, 1,1,2,3,3,3-hexafluoropropylene using B2PLYP functional (basis sets are: aug-cc-pVDZ and aug-cc-pVTZ) and M06-2x functional (6–311++G**...

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Veröffentlicht in:Monatshefte für Chemie 2022-08, Vol.153 (7-8), p.609-621
Hauptverfasser: Krisyuk, Boris E., Mayorov, Alexey V., Mamin, Eldar A.
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Sprache:eng
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Zusammenfassung:Quantum-chemical calculations were performed for the primary step of ozonolysis reaction of different olefins: ethylene, 1,3-butadiene, 1,1,2,2-tetrafluoroethylene, 1,1,2,3,3,3-hexafluoropropylene using B2PLYP functional (basis sets are: aug-cc-pVDZ and aug-cc-pVTZ) and M06-2x functional (6–311++G** and 6–311++G(2df,2pd)) in both gas and liquid phases. Solvent influence (water and carbon tetrachloride/tetrachloroethylene) is taken into account using the polarized continuum model (PCM), the solvation model based on density (SMD) and the Onsager model. Rate constants for the different reaction paths of addition were found. The kinetic parameters (activation enthalpy, activation entropy) are found in terms of transition state theory based on consideration of stationary points on potential energy surface. It is shown that the more solvent polarity increases the more solvation and the rate constant increase. Interestingly, this effect takes place for the both Criegee and DeMore addition channels; the last one increases more greatly. Comparisons with experimental data made it possible to estimate the effect of solvation and the cage effect separately for this reaction. Graphical abstract
ISSN:0026-9247
1434-4475
DOI:10.1007/s00706-022-02946-4