A theoretical study of the gas-phase ion pair S(N)2 reactions of lithium halide and methyl halide with inversion and retention mechanisms

doi:10.1016/j.theochem.2003.10.002

	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
	2003-12-15
发表期刊	JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM
ISSN	0166-1280
卷号	664 页码:279-289
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.
关键词	Ion Pair s(n)2 Reaction Identity And non-Identity Inversion And Retention
学科领域	Chemistry, Physical
DOI	10.1016/j.theochem.2003.10.002
收录类别	SCI
语种	英语
WOS研究方向	Chemistry
WOS类目	Chemistry, Physical
WOS记录号	WOS:000187226300027
引用统计	被引频次：11[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://ir.kib.ac.cn/handle/151853/15458
专题	植物化学与西部植物资源持续利用国家重点实验室
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
推荐引用方式 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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