| A theoretical study of the gas-phase ion pair S(N)2 reactions of lithium halide and methyl halide with inversion and retention mechanisms | |
| Xiong, Y; Zhu, HJ; Ren, Y | |
| Corresponding Author | Zhu, HJ (reprint author), Sichuan Univ, Fac Chem, Chengdu 610064, Peoples R China. |
| 2003-12-15 | |
| Source Publication | JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM
 |
| ISSN | 0166-1280 |
| Volume | 664Pages:279-289 |
| Abstract | Identity and non-identity ion pair S(N)2 reactions, LiX + CH3X, LiY + CH3X (Y, X = F, Cl, Br and I) were investigated using CCSD(T) calculations. Two possible reaction mechanisms, inversion and retention, were discussed. Introduction of lithium cation will significantly raise the inversion barriers and may lower the retention barriers. The analysis of barrier gaps between the two channels indicates that the retention mechanism is favorable for all of the reactions involving fluorine, in contrast to the anionic S(N)2 reactions at carbon where inversion reaction pathway is much more favorable for all halogens. The stabilization energies for dipole-dipole complexes (CH3XLiY)-Li-... (Y = F-I) are found to have a good correlation with the electronegativity of X. The CCSD(T) central barriers and overall barriers show good agreement with the predictions of Marcus equation and its modification, respectively. Further interesting feature of the non-identity ion pair S(N)2 reactions is a good correlation between inversion central barriers and the composite geometric looseness (%L). (C) 2003 Elsevier B.V. All rights reserved. |
| Keyword | Ion Pair s(n)2 Reaction Identity And non-Identity Inversion And Retention |
| Subject Area | Chemistry, Physical |
| DOI | 10.1016/j.theochem.2003.10.002 |
| Indexed By | SCI |
| Language | 英语 |
| WOS Research Area | Chemistry |
| WOS Subject | Chemistry, Physical |
| WOS ID | WOS:000187226300027 |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.kib.ac.cn/handle/151853/15458 |
| Collection | 植物化学与西部植物资源持续利用国家重点实验室 |
| Affiliation | 1.Sichuan Univ, Fac Chem, Chengdu 610064, Peoples R China 2.CAS, State Key Lab Phytochem & Plant Resources W China, Kunming 650200, Peoples R China |
| Recommended Citation GB/T 7714 | Xiong, Y,Zhu, HJ,Ren, Y. A theoretical study of the gas-phase ion pair S(N)2 reactions of lithium halide and methyl halide with inversion and retention mechanisms[J]. JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM,2003,664:279-289. |
| APA | Xiong, Y,Zhu, HJ,&Ren, Y.(2003).A theoretical study of the gas-phase ion pair S(N)2 reactions of lithium halide and methyl halide with inversion and retention mechanisms.JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM,664,279-289. |
| MLA | Xiong, Y,et al."A theoretical study of the gas-phase ion pair S(N)2 reactions of lithium halide and methyl halide with inversion and retention mechanisms".JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM 664(2003):279-289. |
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