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Understanding the role of noncovalent interactions on the rate of some Diels‐Alder reactions in different solvents
Author(s) -
Mehranfar Aliyeh,
Izadyar Mohammad,
Khavani Mohammad,
Housaindokht Mohammad Reza
Publication year - 2019
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25878
Subject(s) - cycloaddition , chemistry , van der waals force , solvation , non covalent interactions , gibbs free energy , solvent , covalent bond , polar , solvent effects , computational chemistry , interaction energy , diels–alder reaction , thermodynamics , organic chemistry , molecule , hydrogen bond , catalysis , physics , astronomy
Abstract In this article, the role of noncovalent interactions (NCI) on four types of cycloaddition reactions in different solvents was investigated by employing quantum chemistry calculations. For this purpose, explicit and implicit solvation models were applied in the experimental conditions of temperature and pressure. NCI analysis indicates that van der Waals (vdW) interactions, as a part of NCI, change the stability and Gibbs energy of the transition states (TSs), which in turn affects the rate of the reaction. On the basis of NCI analysis, a partial covalent nature of the forming CC bonds at the TSs was confirmed. Energy analysis confirms that vdW interactions can be considered as the main part of the solute‐solvent interactions in the cycloaddition reactions. Moreover, cycloaddition reactions of the polar reactants are faster in polar solvents, while nonpolar solvents induce a contrast effect on the rate of these reactions.