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231224s2015 xx |||||o 00| ||eng c |
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|a 10.1002/jcc.23862
|2 doi
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|a pubmed25n0823.xml
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|a (DE-627)NLM246984465
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|a (NLM)25760852
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|a DE-627
|b ger
|c DE-627
|e rakwb
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|a eng
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|a Zhao, Wen-Yang
|e verfasserin
|4 aut
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|a Probing the reactivity of microhydrated α-nucleophile in the anionic gas-phase S(N)2 reaction
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|c 2015
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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 28.10.2015
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|a Date Revised 26.03.2015
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|a published: Print-Electronic
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|a Citation Status MEDLINE
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|a © 2015 Wiley Periodicals, Inc.
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|a To probe the kinetic performance of microsolvated α-nucleophile, the G2(+)M calculations were carried out for the gas-phase S(N)2 reactions of monohydrated and dihydrated α-oxy-nucleophiles XO(-)(H2O)(n = 1,2) (X = HO, CH3O, F, Cl, Br), and α-sulfur-nucleophile, HSS(-)(H2O)(n = 1,2), toward CH3Cl. We compared the reactivities of hydrated α-nucleophiles to those of hydrated normal nucleophiles. Our calculations show that the α-effect of monohydrated and dihydrated α-oxy-nucleophiles will become weaker than those of unhydrated ones if we apply a plot of activation barrier as a function of anion basicity. Whereas the enhanced reactivity of monohydrated and dihydrated ROO(-) (R = H, Me) could be observed if compared them with the specific normal nucleophiles, RO(-) (R = H, Me). This phenomena can not be seen in the comparisons of XO(-)(H2O)(n = 1,2) (X = F, Cl, Br) with ClC2H4O(-)(H2O)(n = 1,2), a normal nucleophile with similar gas basicity to XO(-)(H2O)(n = 1,2). These results have been carefully analyzed by natural bond orbital theory and activation strain model. Meanwhile, the relationships between activation barriers with reaction energies and the ionization energies of α-nucleophile are also discussed
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|a Journal Article
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|a Research Support, Non-U.S. Gov't
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|a activation strain model
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|a alpha-effect
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|a gas basicity
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|a gas-phase SN2 reaction
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|a microhydrated nucleophile
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|a Gases
|2 NLM
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|a Nitro Compounds
|2 NLM
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|a Water
|2 NLM
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|a 059QF0KO0R
|2 NLM
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|a Sulfur
|2 NLM
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|a 70FD1KFU70
|2 NLM
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| 700 |
1 |
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|a Yu, Jie
|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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1 |
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|a Wei, Xi-Guang
|e verfasserin
|4 aut
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1 |
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|a Qiu, Fang-Zhou
|e verfasserin
|4 aut
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1 |
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|a Li, Peng-Hui
|e verfasserin
|4 aut
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|a Li, He
|e verfasserin
|4 aut
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|a Zhou, Yi-Peng
|e verfasserin
|4 aut
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|a Yin, Chang-Zhen
|e verfasserin
|4 aut
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|a Chen, An-Pu
|e verfasserin
|4 aut
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|a Li, Hao
|e verfasserin
|4 aut
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1 |
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|a Zhang, Lei
|e verfasserin
|4 aut
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|a Zhu, Jun
|e verfasserin
|4 aut
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| 700 |
1 |
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|a Ren, Yi
|e verfasserin
|4 aut
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|a Lau, Kai-Chung
|e verfasserin
|4 aut
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| 773 |
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|i Enthalten in
|t Journal of computational chemistry
|d 1984
|g 36(2015), 11 vom: 30. Apr., Seite 844-52
|w (DE-627)NLM098138448
|x 1096-987X
|7 nnns
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| 773 |
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|g volume:36
|g year:2015
|g number:11
|g day:30
|g month:04
|g pages:844-52
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|u http://dx.doi.org/10.1002/jcc.23862
|3 Volltext
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|d 36
|j 2015
|e 11
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|h 844-52
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