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231224s2013 xx |||||o 00| ||eng c |
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|a 10.1002/jcc.23356
|2 doi
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|a pubmed24n0761.xml
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|a (DE-627)NLM228496454
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|a (NLM)23784794
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|a DE-627
|b ger
|c DE-627
|e rakwb
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|a eng
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| 100 |
1 |
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|a Ren, Yi
|e verfasserin
|4 aut
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|a The α-effect exhibited in gas-phase S(N)2@N and S(N)2@C reactions
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|c 2013
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|a Text
|b txt
|2 rdacontent
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|a ƒaComputermedien
|b c
|2 rdamedia
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|a ƒa Online-Ressource
|b cr
|2 rdacarrier
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|a Date Completed 04.02.2014
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|a Date Revised 24.07.2013
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|a published: Print-Electronic
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|a Citation Status MEDLINE
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|a © 2013 Wiley Periodicals, Inc.
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|a In order to explore the existence of α-effect in gas-phase S(N)2N reactions, and to compare its similarity and difference with its counterpart in S(N)2@C reactions, we have carried out a theoretical study on the reactivity of six α-oxy-Nus (FO(-), ClO(-), BrO(-), HOO(-), HSO(-), H2NO(-)) in the S(N)2 reactions toward NR2Cl (R = H, Me) and RCl (R = Me, i-Pr) using the G2(+)M theory. An enhanced reactivity induced by the α-atom is found in all examined systems. The magnitude of the α-effect in the reactions of NR2Cl (R = H, Me) is generally smaller than that in the corresponding S(N)2 reaction, but their variation trend with the identity of α-atom is very similar. The origin of the α-effect of the S(N)2@N reactions is discussed in terms of activation strain analysis and thermodynamic analysis, indicating that the α-effect in the S(N)2@N reactions largely arises from transition state stabilization, and the "hyper-reactivity" of these α-Nus is also accompanied by an enhanced thermodynamic stability of products from the n(N) → σ*(O-Y) negative hyperconjugation. Meanwhile, it is found that the reactivity of oxy-Nus in the S(N)2 reactions toward NMe2Cl is lower than toward i-PrCl, which is different from previous experiments, that is, the S(N)2 reactions of NH2Cl is more facile than MeCl
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|a Journal Article
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|a Research Support, Non-U.S. Gov't
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|a NBO analysis
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|a activation strain analysis
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|a reactivity of oxy-nucleophile
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|a α-effect in gas-phase SN2@N and SN2@C reactions
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|a Anions
|2 NLM
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|a Gases
|2 NLM
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|a Carbon
|2 NLM
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|a 7440-44-0
|2 NLM
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|a Nitrogen
|2 NLM
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|a N762921K75
|2 NLM
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| 700 |
1 |
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|a Wei, Xi-Guang
|e verfasserin
|4 aut
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| 700 |
1 |
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|a Ren, Si-Jia
|e verfasserin
|4 aut
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| 700 |
1 |
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|a Lau, Kai-Chung
|e verfasserin
|4 aut
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| 700 |
1 |
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|a Wong, Ning-Bew
|e verfasserin
|4 aut
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| 700 |
1 |
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|a Li, Wai-Kee
|e verfasserin
|4 aut
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| 773 |
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|i Enthalten in
|t Journal of computational chemistry
|d 1984
|g 34(2013), 23 vom: 05. Sept., Seite 1997-2005
|w (DE-627)NLM098138448
|x 1096-987X
|7 nnns
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| 773 |
1 |
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|g volume:34
|g year:2013
|g number:23
|g day:05
|g month:09
|g pages:1997-2005
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|u http://dx.doi.org/10.1002/jcc.23356
|3 Volltext
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