Gas-phase non-identity S(N)2 reactions at neutral nitrogen: a hybrid DFT study
Yang, J ; Ren, Y ; Zhu, HJ ; Chu, SY
2003
发表期刊INTERNATIONAL JOURNAL OF MASS SPECTROMETRY
ISSN1387-3806
卷号229期号:3页码:199-208
摘要The gas-phase non-identity nucleophilic substitution reactions at saturated nitrogen Y-+ NH2X --> NH2Y + X- (Y, X = F, Cl, Br and I) were evaluated at the level of MPW1K/6-31+G(d, p). The enthalpies of reactions are exothermic only when the nucleophile is the lighter halide. Central barriers (DeltaH(YX)(not equal)) for reactions in the exothermic direction are slightly higher than the corresponding barriers at carbon. The lower overall barriers relative to the reactants (DeltaH(YX)(b)) than the corresponding reactions at carbon suggest that S(N)2 reactions at nitrogen may be more facile than at carbon. Both the central barriers (AH(YX)(not equal)) and the overall barriers (DeltaH(YX)(b)) correlate well with reaction exothermicity. Further interesting features of the non-identity reactions at nitrogen are the reasonable correlation between the central barriers (DeltaH(YX)(not equal)) with the composite geometrical looseness (%L-not equal), geometrical asymmetry (%AS(not equal)), and charge asymmetry of the transition structures (Deltaq (X - Y)). The data for the central barriers and the overall barriers show good agreement with the prediction of the Marcus equation and its modification, respectively. Kinetic and thermodynamic investigations predict that the nucleophilicity of X- in the S(N)2 at nitrogen decreases in the order F- < Cl- < Br- < I-, the leaving-group ability increases in the order F > Cl > Br > I. (C) 2003 Elsevier B.V. All rights reserved.
关键词s(n)2 At Neutral Nitrogen Hybrid Dft Method Reaction Mechanism Nucleophilicity Transition-state Geometries Nucleophilic-substitution Methyl Halides Sn2 Reactions Anions Displacement Barriers
学科领域Physics, Atomic, Molecular & Chemical ; Spectroscopy
收录类别sci
语种英语
文献类型期刊论文
条目标识符http://ir.kib.ac.cn/handle/151853/15462
专题植物化学与西部植物资源持续利用国家重点实验室
推荐引用方式
GB/T 7714
Yang, J,Ren, Y,Zhu, HJ,et al. Gas-phase non-identity S(N)2 reactions at neutral nitrogen: a hybrid DFT study[J]. INTERNATIONAL JOURNAL OF MASS SPECTROMETRY,2003,229(3):199-208.
APA Yang, J,Ren, Y,Zhu, HJ,&Chu, SY.(2003).Gas-phase non-identity S(N)2 reactions at neutral nitrogen: a hybrid DFT study.INTERNATIONAL JOURNAL OF MASS SPECTROMETRY,229(3),199-208.
MLA Yang, J,et al."Gas-phase non-identity S(N)2 reactions at neutral nitrogen: a hybrid DFT study".INTERNATIONAL JOURNAL OF MASS SPECTROMETRY 229.3(2003):199-208.
条目包含的文件
文件名称/大小 文献类型 版本类型 开放类型 使用许可
2012101834.pdf(273KB) 开放获取--请求全文
个性服务
推荐该条目
保存到收藏夹
查看访问统计
导出为Endnote文件
谷歌学术
谷歌学术中相似的文章
[Yang, J]的文章
[Ren, Y]的文章
[Zhu, HJ]的文章
百度学术
百度学术中相似的文章
[Yang, J]的文章
[Ren, Y]的文章
[Zhu, HJ]的文章
必应学术
必应学术中相似的文章
[Yang, J]的文章
[Ren, Y]的文章
[Zhu, HJ]的文章
相关权益政策
暂无数据
收藏/分享
所有评论 (0)
暂无评论
 

除非特别说明,本系统中所有内容都受版权保护,并保留所有权利。