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 AuthorZhu, HJ (reprint author), Sichuan Univ, Fac Chem, Chengdu 610064, Peoples R China.
2003-12-15
Source PublicationJOURNAL OF MOLECULAR STRUCTURE-THEOCHEM
ISSN0166-1280
Volume664Pages:279-289
AbstractIdentity 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.
KeywordIon Pair s(n)2 Reaction Identity And non-Identity Inversion And Retention
Subject AreaChemistry, Physical
DOI10.1016/j.theochem.2003.10.002
Indexed BySCI
Language英语
WOS Research AreaChemistry
WOS SubjectChemistry, Physical
WOS IDWOS:000187226300027
Citation statistics
Document Type期刊论文
Identifierhttp://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
Affiliation1.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.
Files in This Item: Download All
File Name/Size DocType Version Access License
2012101832.pdf(205KB) 开放获取--View Download
Related Services
Recommend this item
Bookmark
Usage statistics
Export to Endnote
Google Scholar
Similar articles in Google Scholar
[Xiong, Y]'s Articles
[Zhu, HJ]'s Articles
[Ren, Y]'s Articles
Baidu academic
Similar articles in Baidu academic
[Xiong, Y]'s Articles
[Zhu, HJ]'s Articles
[Ren, Y]'s Articles
Bing Scholar
Similar articles in Bing Scholar
[Xiong, Y]'s Articles
[Zhu, HJ]'s Articles
[Ren, Y]'s Articles
Terms of Use
No data!
Social Bookmark/Share
File name: 2012101832.pdf
Format: Adobe PDF
This file does not support browsing at this time
All comments (0)
No comment.
 

Items in the repository are protected by copyright, with all rights reserved, unless otherwise indicated.