Microsolvation effects on the reactivity of oxy-nucleophiles : the case of gas-phase SN2 reactions of YO(CH3OH)n=1,2 towards CH3Cl

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Author(s)

Detail(s)

Original languageEnglish
Article number192
Journal / PublicationJournal of Molecular Modeling
Volume23
Issue number192
Online published20 May 2017
Publication statusPublished - Jun 2017

Abstract

The modified G4(MP2) method was applied to explore microsolvation effects on the reactivity of four solvated normal oxy-nucleophiles YO(CH3OH)n=1,2 (Y = CH3, C2H5, FC2H4, ClC2H4), and five α-oxy-nucleophiles YO(CH3OH)n=1,2 (Y = HO, CH3O, F, Cl, Br), in gas-phase SN2 reactions towards the substrate CH3Cl. Based on a Brønsted-type plot, our calculations reveal that the overall activation barriers of five microsolvated α-oxy-nucleophiles are obviously smaller than the prediction from the correlation line constructed by four normal microsolvated ones to different degrees, and clearly demonstrate the existence of an α-effect in the presence of one or two methanol molecule(s). Moreover, it was found that the α-effect of the mono-methanol microsolvated α-nucleophile is stronger than that of the monohydrated α-nucleophile. However, the α-effect of YO(CH3OH)2 becomes weaker for Y = HO and CH3O, whereas it becomes stronger for Y = F, Cl, Br than that of YO(H2O)2, which can be explained by analyses of the activation strain model in the two cases. It was also found that the rationale about the low ionization energy of α-nucleophile inducing the α-effect was not widely significant. [Figure not available: see fulltext.].

Research Area(s)

  • Methanol-microsolvation, Modified G4(MP2) method, Oxy-nucleophiles, Reactivity, SN2 reactions

Citation Format(s)

Microsolvation effects on the reactivity of oxy-nucleophiles : the case of gas-phase SN2 reactions of YO(CH3OH)n=1,2 towards CH3Cl. / Yun-Yun, Liu; Fang-Zhou, Qiu; Jun, Zhu; Yi, Ren; Kai-Chung, Lau.

In: Journal of Molecular Modeling, Vol. 23, No. 192, 192, 06.2017.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review