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DFT study on the reactions of ClO–/BrO– with RCl (R = CH3, C2H5, and C3H7) in gas phase

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Abstract

Gas-phase reactions of ClO–/BrO– with RCl (R = CH3, C2H5, and C3H7) have been investigated in detail using the popular DFT functional BHandHLYP/aug-cc-pVDZ level of theory. As a result, our findings strongly suggest that the type of reaction is firstly initiated by a typical SN2 fashion. Subsequently, two competitive substitution steps, named as SN2-induced substitution and SN2-induced elimination, respectively, would proceed before the initial SN2 product ion-dipole complex separates, in which the former exhibits less reactivity than the latter. Those are consistent with relevant experimental results. Moreover, we have also explored reactivity difference for the title reactions in term of some factors derived from methyl group, p-π electronic conjugation, ionization energy (IE), as well as molecular orbital (MO) analysis.

Energy profiles for the ClO– reactions and BrO–reactions, respectively

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Project supported: The Scientific and Technical Project Supported by Gansu Province (Project No. 090GKCA027), The Scientific and Technical Project of Lanzhou City (Project No. 2009-1-167), Science Fund of Public Welfare Meteorological Organization (Project No. GYHY200806021 and GYHY201106029), National Basic Research Program of China (Project No. 2012CB955304), the National Key Natural Science Fund (Project No. 40830957), and National Natural Science Fund (Project No. 41261052).

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Authors and Affiliations

  1. College of Chemical Engineering, Northwest University for Nationalities, Lanzhou, Gansu, 730030, China

    Liang Junxi, Wang Yanbin & Li Yu

  2. Institute of Arid Meteorology, CMA; Key laboratory of Arid Climatic Change and Reducing Disaster of Gansu Province, Key Open Laboratory of Arid Climatic Change and Disaster Reduction of CMA, Lanzhou, 730020, China

    Zhang Qiang

  3. Gansu Key Laboratory of Polymer Materials, College of Chemistry and Chemical Engineering, Key Laboratory of Eco-environment-related Polymer Materials; Ministry of Education, Northwest Normal University, Lanzhou, Gansu, 730070, China

    Geng Zhiyuan & Wang Xiuhong

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  1. Liang Junxi
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  2. Wang Yanbin
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  3. Zhang Qiang
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  4. Li Yu
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  5. Geng Zhiyuan
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Correspondence to Wang Yanbin or Zhang Qiang.

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Junxi, L., Yanbin, W., Qiang, Z. et al. DFT study on the reactions of ClO–/BrO– with RCl (R = CH3, C2H5, and C3H7) in gas phase. J Mol Model 19, 1739–1750 (2013). https://doi.org/10.1007/s00894-012-1736-1

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  • DOI: https://doi.org/10.1007/s00894-012-1736-1

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