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题名: A theoretical study of the gas-phase ion pair S(N)2 reactions of lithium halide and methyl halide with inversion and retention mechanisms
作者: Xiong, Y; Zhu, HJ; Ren, Y
刊名: JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM
关键词: ion pair ; S(N)2 reaction ; identity and non-identity ; inversion and retention
英文摘要: 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.
出版日期: 2003-12-15
卷号: 664, 页码:279-289
语种: 英语
收录类别: SCI
学科分类: Chemistry, Physical
ISSN号: 0166-1280
Citation statistics:
内容类型: 期刊论文
URI标识: http://ir.kib.ac.cn/handle/151853/15458
Appears in Collections:植物化学与西部植物资源持续利用国家重点实验室_期刊论文

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作者单位: 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:
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,JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM,2003,664():279-289
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