A Comprehensive Study of the Solvent Effects on the Cycloaddition Reaction of Diethyl Azodicarboxylate and Ethyl Vinyl Ether: Efficient Implementation of QM and TD-DFT Study

作者：Khavani Mohammad^*; Izadyar Mohammad

来源：International Journal of Quantum Chemistry, 2015, 115(6): 381-388.

DOI：10.1002/qua.24853

• transition state
• chemical reactivity
• electron density
• charge transfer
• dipole moment
• activation energy

In this work, quantum chemistry calculations performed to study the kinetics and thermodynamic parameters of [2+2] cycloaddition reaction of diethyl azodicarboxylate and ethyl vinyl ether in eighty-three solvents and gas phase. The solvent effect on the reaction path and electron density of the C2N6 critical bond as the reaction coordinate at the TS was investigated. Calculated rate constants in various solvents showed that increase in the activation dipole moment accelerates the reaction. Based on the time-dependent studies, using a conductor like polarizable continuum model solvation model, the solvent effects on the excitation energies of the reactants and transition states (TSs) and the corresponding chemical shifts were analyzed. Finally, some correlations between the rate constant and quantum reactivity indices such as electrophilicity index, chemical hardness, and electronic chemical potential were investigated.

• 出版日期2015-3-15