Quantum chemistry aspects of the solvent effects on the ene reaction of 1‐Phenyl‐1, 3, 4‐triazolin‐2, 5‐dione and 2‐methyl‐2‐butene. Issue 10 (24th February 2014)

• Record Type: Journal Article
• Authors: Izadyar, Mohammad; Khavani, Mohammad
• Is Part Of: International journal of quantum chemistry. Volume 114:Issue 10(2014:May 15)
• Page Start: 666
• Page End: 674
• Publication Date: 2014-02-24
• Subjects: Quantum chemistry -- Periodicals; 541.28
• DOI: 10.1002/qua.24652
• Languages: English
• ISSNs: 0020-7608

Abstract

<abstract abstract-type="main"> <title> <x xml:space="preserve">Abstract</x> </title> <p>A density functional theory study was used to investigate the quantum aspects of the solvent effects on the kinetic and mechanism of the ene reaction of 1‐phenyl‐1, 3, 4‐triazolin‐2, 5‐dione and 2‐methyl‐2‐butene. Using the B3LYP/6–311++ G(d, p) level of the theory, reaction rates have been calculated in the various solvents and good agreement with the experimental data has been obtained. Natural bond orbital analysis has been applied to calculate the stabilization energy of N18H19 bond during the reaction. Topological analysis of quantum theory of atom in molecule (QTAIM) studies for the electron charge density in the bond critical point (BCP) of N18H19 bond of the transition states (TSs) in different solvents shows a linear correlation with the interaction energy. It is also seen form the QTAIM analysis that increase in the electron density in the BCP of N18H19, raises the corresponding vibrational frequency. Average calculated ratio of 0.37 for kinetic energy density to local potential energy density at the BCPs as functions of N18H19 bond length in different media confirmed covalent nature of this bond. Using the concepts of the global electrophilicity index, chemical hardness and electronic chemical potentials, some correlations with the rate constants and interaction energy have been established. Mechanism and kinetic studies on 1‐phenyl‐1, 3, 4‐triazolin‐2, 5‐dione and 2‐methyl‐2‐butene ene reaction suggests that the reaction rate will boost with interaction energy enhancement. Interaction energy of the TS depends on the solvent nature and is directly related to electron density of the bonds involved in the reaction proceeding, global electrophilicity index and electronic chemical potential. However, the chemical hardness relationship is reversed. Finally, an interesting and direct correlation between the imaginary vibrational frequency of the N18H19 critical bond and its electron density at the TS has been obtained. © 2014 Wiley Periodicals, Inc.</p> </abstract>