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Torsion potentials and electronic structure of trifluoromethoxy- and trifluoromethylthiobenzene: an ab initio study
Authors:Evgenij G KapustinVladimir M Bzhezovsky  Lev M Yagupolskii
Institution:Institute of Organic Chemistry, National Academy of Science of Ukraine, Murmanskaya 5, 02094 Kiev-94, Ukraine
Abstract:Potential functions of internal rotation about the Csp2X bonds in molecules C6H5XCF3 (X=O, S) were calculated at the second-order Møller-Plesset perturbation level of theory with 6-31G(d) basis set. The profile of the potential function and the rotation barrier (ΔE#=3.0 kJ/mol) found for C6H5OCF3 suggest that, depending on experimental conditions, there can be either free rotation about the Csp2O bond or the conformational equilibrium is shifted to the side of the orthogonal form. The rotational barrier for C6H5SCF3 is 14.7 kJ/mol and the molecule exists in the stable orthogonal conformation. The nature of hybridization, energy and population of lone electron pairs (LPs) on the oxygen and sulfur atoms were considered by using the Natural Bond Orbital (NBO) method. The energy of interactions of the LPs with antibonding π-orbitals of the aromatic moiety were estimated for different conformations. The distribution of electron density in the molecules was discussed. The results were compared with analogous calculations on the molecules C6H5XCH3.
Keywords:Ab initio  Trifluoromethoxybenzene  Trifluoromethylthiobenzene  Methoxybenzene  Methylthiobenzene  Conformations  NBO analysis
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