Substituent effects on the S–H bond dissociation energies of thiophenols
作者： Yao Fu , Bo-Lin Lin , Ke-Sheng Song , Lei Liu , Qing-Xiang Guo
DOI: 10.1039/B201003H
关键词: Substituent 、 Dissociation (chemistry) 、 Physical chemistry 、 Isodesmic reaction 、 Chemistry 、 Computational chemistry 、 Bond-dissociation energy 、 Thiophenol 、 Hydrogen bond 、 Radical 、 Homolysis
摘要: Density function UB3LYP/6-311++g(d,p) and perturbation theory ROMP2/6-311++g(d,p) calculations were performed on 4-substituted thiophenols their corresponding radicals. It was found that although UB3LYP ROMP2 methods underestimated the absolute S–H bond dissociation energies, they could predict almost as good relative energies a method of considerably higher level, UCCSD(T)/6-311++g(d,p). From calculation results it determined should have positive correlation with substituent σp+ constants whose slope ca. 2.5 kcal mol−1. Such indicated experimental obtained from previous solution phase measurement reasonably accurate for para H, CH3, OCH3, Cl, and NO2 substituted thiophenols. However, energy 4-aminothiophenol too low, which by in this study to be caused hydrogen bonding between amino group solvent molecules. Finally, through studies isodesmic reactions effects stability neutral had fair constants; 0.5 On other hand, thiophenol radicals an excellent negative gave −1.8 Therefore, major source homolysis products, namely,
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