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

Journal of Molecular Modeling volume 23, Article number: 192 (2017) Cite this article

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.

Variation of alpha-effect in the gas-phase SN2 reaction with the microsolvation

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Acknowledgments

This work was supported by National Natural Science Foundation of China (No.J1310008), Strategic Research Grants from City University of Hong Kong (No. 7004403), the Open Research Fund of State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University (No. 201511), and the Open Research Fund of Key Laboratory of Advanced Scientific Computation, Xihua University (No. szjj2013-024).

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Authors and Affiliations

  1. College of Chemistry and Key State Laboratory of Biotherapy, Sichuan University, Chengdu, 610064, China

    Liu Yun-Yun, Qiu Fang-Zhou & Ren Yi

  2. State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry and Department of Chemistry, Xiamen University, Xiamen, 361005, China

    Zhu Jun

  3. Department of Biology and Chemistry, City University of Hong Kong, Kowloon, Hong Kong

    Lau Kai-Chung

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  1. Liu Yun-Yun
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  2. Qiu Fang-Zhou
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  3. Zhu Jun
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  4. Ren Yi
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  5. Lau Kai-Chung
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Correspondence to Ren Yi or Lau Kai-Chung.

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Cartesian coordinates and natural population charge distributions of all reactants and TS structures, This material is available free of charge via the internet. (DOCX 317 kb)

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Yun-Yun, L., Fang-Zhou, Q., Jun, Z. et al. Microsolvation effects on the reactivity of oxy-nucleophiles: the case of gas-phase SN2 reactions of YO−(CH3OH) n=1,2 towards CH3Cl. J Mol Model 23, 192 (2017). https://doi.org/10.1007/s00894-017-3351-7

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  • DOI: https://doi.org/10.1007/s00894-017-3351-7

Keywords

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