| Theoretical investigation of ion pair S(N)2 reactions of alkali isothiocyanates with alkyl halides. Part 1. Reaction of lithium isothiocyanate and methyl fluoride with inversion mechanism |
| Zhu, HJ
; Ren, Y
; Ren, J
; Chu, SY
|
| 通讯作者 | Ren, Y (reprint author), Sichuan Univ, Coll Chem, Chengdu 610064, Peoples R China. yiren57@hotmail.com
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| 2005
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| 发表期刊 | INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
 |
| ISSN | 0020-7608
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| 卷号 | 101期号:1页码:104-112 |
| 摘要 | The gas-phase ionic S(N)2 reactions NCS- + CH3F and ion pair S(N)2 reaction LiNCS + CH3F with inversion mechanism were investigated at the level of MP2(full)/6-311+G**//HF/6-311+G**. Both of them involve the reactants complex, inversion transition state, and products complex. There are two possible reaction pathways in the ionic S(N)2 reaction but four reaction pathways in the ion pair S(N)2 reaction. Our results indicate that the introduction of lithium significantly lower the reaction barrier and make the ion pair displacement reaction more facile. For both ionic and ion pair reaction, methyl thiocyanate is predicted to be the major product, but the latter is more selective. More-stable methyl isothiocyanate can be prepared by thermal rearrangement of methyl thiocyanate. The theoretical predictions are consistent with the known experimental results. (C) 2004 Wiley Periodicals, Inc. |
| 关键词 | Ab Initio
Inversion Mechanism
Isothiocyanate
Reaction Pathway
s(n)2
Thiocyanate
Transition-state Structure
Nucleophilic-substitution Reactions
Retention Mechanisms
Configuration
|
| 学科领域 | Chemistry, Physical
; Mathematics, Interdisciplinary Applications
; Physics, Atomic, Molecular & Chemical
|
| 收录类别 | sci
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| 语种 | 英语
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| 文献类型 | 期刊论文
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| 条目标识符 | http://ir.kib.ac.cn/handle/151853/15442
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| 专题 | 植物化学与西部植物资源持续利用国家重点实验室
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推荐引用方式
GB/T 7714 |
Zhu, HJ,Ren, Y,Ren, J,et al. Theoretical investigation of ion pair S(N)2 reactions of alkali isothiocyanates with alkyl halides. Part 1. Reaction of lithium isothiocyanate and methyl fluoride with inversion mechanism[J]. INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY,2005,101(1):104-112.
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| APA |
Zhu, HJ,Ren, Y,Ren, J,&Chu, SY.(2005).Theoretical investigation of ion pair S(N)2 reactions of alkali isothiocyanates with alkyl halides. Part 1. Reaction of lithium isothiocyanate and methyl fluoride with inversion mechanism.INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY,101(1),104-112.
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| MLA |
Zhu, HJ,et al."Theoretical investigation of ion pair S(N)2 reactions of alkali isothiocyanates with alkyl halides. Part 1. Reaction of lithium isothiocyanate and methyl fluoride with inversion mechanism".INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 101.1(2005):104-112.
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