| Автор | Fu, Yao |
| Автор | Lin, Bo-Lin |
| Автор | Song, Ke-Sheng |
| Автор | Liu, Lei |
| Автор | Guo, Qing-Xiang |
| Дата выпуска | 2002 |
| dc.description | Density function UB3LYP/6-311++g(d,p) and perturbation theory ROMP2/6-311++g(d,p) calculations were performed on 4-substituted thiophenols and their corresponding radicals. It was found that although UB3LYP and ROMP2 methods underestimated the absolute Sâ H bond dissociation energies, they could predict almost as good relative Sâ H bond dissociation energies as a method of a considerably higher level, UCCSD(T)/6-311++g(d,p). From the calculation results it was determined that the Sâ H bond dissociation energies of thiophenols should have a positive correlation with the substituent Ï p<sup>+</sup> constants whose slope was ca. 2.5 kcal mol<sup>â 1</sup>. Such a slope indicated that the experimental Sâ H bond dissociation energies obtained from a previous solution phase measurement were reasonably accurate for para H, CH3, OCH3, Cl, and NO2 substituted thiophenols. However, the solution phase bond dissociation energy for 4-aminothiophenol was too low, which was found by the calculation in this study to be caused by the hydrogen bonding between the amino group and the solvent molecules. Finally, through the studies on the isodesmic reactions it was found that the substituent effects on the stability of neutral thiophenols had a fair and positive correlation with the substituent Ï p<sup>+</sup> constants; the slope was 0.5 kcal mol<sup>â 1</sup>. On the other hand, the substituent effects on the stability of thiophenol radicals had an excellent and negative correlation with the substituent Ï p<sup>+</sup> constants and gave a slope of â 1.8 kcal mol<sup>â 1</sup>. Therefore, the major source of the substituent effects on Sâ H bond dissociation energies of thiophenols was the stability of the homolysis products, namely, thiophenol radicals. |
| Формат | application.pdf |
| Издатель | Royal Society of Chemistry |
| Название | Substituent effects on the S–H bond dissociation energies of thiophenolsElectronic supplementary information (ESI) available: detailed results of the bond lengths, charge and spin distributions, and vibration frequencies. See http://www.rsc.org/suppdata/p2/b2/b201003h/ |
| Тип | research-article |
| DOI | 10.1039/b201003h |
| Electronic ISSN | 1364-5471 |
| Print ISSN | 0300-9580 |
| Журнал | Journal of the Chemical Society, Perkin Transactions 2 |
| Первая страница | 1223 |
| Последняя страница | 1230 |
| Аффилиация | Fu Yao; Department of Chemistry, University of Science and Technology of China |
| Аффилиация | Lin Bo-Lin; Department of Chemistry, University of Science and Technology of China |
| Аффилиация | Song Ke-Sheng; Department of Chemistry, University of Science and Technology of China |
| Аффилиация | LiuPresent address: Department of Chemistry, Columbia University, New York, NY 10027, USA. Lei; Department of Chemistry, University of Science and Technology of China |
| Аффилиация | Guo Qing-Xiang; Department of Chemistry, University of Science and Technology of China |
| Выпуск | 7 |
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