The Effect of Inert Salts on the Structure of the Transition State in the SN2 Reaction between Thiophenoxide Ion and Butyl Chloride
| العنوان: | The Effect of Inert Salts on the Structure of the Transition State in the SN2 Reaction between Thiophenoxide Ion and Butyl Chloride |
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| المؤلفون: | Kenneth Charles Westaway, Yao-ren Fang, Ying Gao |
| المصدر: | The Journal of Organic Chemistry. 68:3084-3089 |
| بيانات النشر: | American Chemical Society (ACS), 2003. |
| سنة النشر: | 2003 |
| مصطلحات موضوعية: | chemistry.chemical_classification, Chemistry, Organic Chemistry, Inorganic chemistry, Leaving group, Salt (chemistry), chemistry.chemical_element, Chloride, Nucleophile, Kinetic isotope effect, medicine, Chlorine, SN2 reaction, Butyl chloride, medicine.drug |
| الوصف: | The effect of inert salts on the structure of the transition state has been determined by measuring the secondary alpha deuterium and the chlorine leaving group kinetic isotope effects for the S(N)2 reaction between n-butyl chloride and thiophenoxide ion in both methanol and DMSO. The smaller secondary alpha deuterium isotope effects and very slightly larger chlorine isotope effects found in both solvents when the inert salt is present suggests that the S(N)2 transition state is tighter and more product-like, with a shorter S-C(alpha) and very a slightly longer C(alpha)-Cl bond when the added salt is present. The salt effect on the reaction in methanol where the reacting nucleophile is the solvent-separated ion-pair complex is much greater than the salt effect on the reaction in DMSO where the reacting nucleophile is the free ion. This greater change in transition-state structure found when the inert salt is present in methanol is consistent with the solvation rule for S(N)2 reactions. The greater change in the S-C(alpha) bond is predicted by the bond strength hypothesis. A rationale for the changes found in transition-state structure when the inert salt is present is suggested for both the free-ion and the ion-pair reactions. |
| تدمد: | 1520-6904 0022-3263 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::c9de41d778a8dd89fe8fdfff6faaaf95 https://doi.org/10.1021/jo026879d |
| رقم الأكسشن: | edsair.doi.dedup.....c9de41d778a8dd89fe8fdfff6faaaf95 |
| قاعدة البيانات: | OpenAIRE |
Find this issue from the American Chemical Society | تدمد: | 15206904 00223263 |
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