1 research outputs found
Quantum Chemistry Aspects of the Solvent Effects on 3,4-Dimethyl-2,5-dihydrothiophen-1,1-dioxide Pyrolysis Reaction
A theoretical density functional
theory (DFT) study was employed
to investigate solvent effects on a retro-cheletropic ene reaction.
The use of a nonpolar solvent in this retro-ene reaction is desirable
to improve the reaction rate. Interactions between 14 different solvents
and the reaction mixtures (reactant and transition state) were considered
using DFT solvation calculations. These results were used to determine
the role of solvents on the rate constants. Theoretical calculations
at the B3LYP/6-311++GÂ(d,p) level revealed that in the presence of
solvents with low polarity the reaction becomes faster, which is in
accordance with experimental data. Transition state–solvent
interactions were analyzed by the quantum theory of atoms in molecules
(QTAIM) and natural bond orbital (NBO) analysis. Finally, several
correlations between electron densities in bond critical points of
the C–S bond and interaction energy as well as vibrational
frequencies at the transition state have been investigated