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Exploring the H-abstraction reactions of CHCl·−/CCl ·−2 with CX3H (X = F, Cl, Br and I) using the density functional theory method

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Abstract

Gas-phase hydrogen abstraction reactions have been compared using the popular density functional theory (DFT) functional BHandHLYP/aug-cc-pVTZ/RECP level of theory, on the basis of the model reaction CHCl·−/CCl ·−2 + CX3H (X = F, Cl, Br and I). Our theoretical findings suggest the efficiency of the H-abstraction reactions induced by either CHCl·− or CCl ·−2 increases as the substrate is changed from CF3H to CI3H, and that CHCl·− has a higher activity in hydrogen abstraction than CCl ·−2 for a given substrate. The entropy effect at 298 K does not significantly change the trend in reactivity of the various reactions, which is in general controlled by the heights of activation energies ΔE ≠. Therefore, we have explored the origin of the energy barriers ΔE ≠ of the reactions using the activation strain model of chemical reactivity.

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Authors and Affiliations

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

    JunXi Liang & YanBin Wang

  2. 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, 730070, China

    ZhiYuan Geng

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  2. YanBin Wang
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Correspondence to JunXi Liang.

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Liang, J., Wang, Y. & Geng, Z. Exploring the H-abstraction reactions of CHCl·−/CCl ·−2 with CX3H (X = F, Cl, Br and I) using the density functional theory method. Sci. China Chem. 55, 1384–1394 (2012). https://doi.org/10.1007/s11426-012-4596-8

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