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Theoretical investigation on the substituent effects of the C–H/π interaction

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Abstract

The substituent effects of C–H/π non-covalent interactions between the C–H bond of alkane/alkene/alkyne/alkane halide and π orbitals of aromatic compounds were studied using the theoretical calculation methods at the CCSD(T)/aug-cc-pvdz level. The natural bond orbital (NBO) analysis implies the charge transfer from the π-system to the C–H bond in the C–H/π interaction. Therefore, either electron-donating group on the π-system or the electron-withdrawing group on the C–H system could enhance the C–H/π interaction. Meanwhile, the substituent effect of the π-system is weaker than that of the C–H systems. There is a good linear correlation between the stabilization energy (energy difference between the C–H/π complex and the separated reactants) and the reaction enthalpy (for the formation of the C–H/π complex) of the alkane/alkene/alkyne-aromatic systems. For the C–H/π interactions between two aromatic systems, good linear correlations were observed between the σp (C–H/π bond pair substituent constant) and the stabilization energy or the r(CH…η), i.e., the distance from H atom to the center of benzene ring.

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Acknowledgements

We thank the Natural Science Foundation of China (No. 31570024) and the Key Research Project of Natural Science Foundation of Anhui Provincial Universities (Nos. KJ2018A0161, KJ2019A0216) for financial supports, the Shanghai Supercomputer Centre for technical support and National Supercomputing Centre in Shenzhen for providing the computational resources and Gaussian 09 (version D01).

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  1. Department of Applied Chemistry, Anhui Agricultural University, Hefei, 230036, Anhui, People’s Republic of China

    Yan Tian, Li Wang, Guoni Fu, Chunyan Zhang & Ruili Lu

  2. School of Chemistry and Chemical Engineering, Hefei Normal University, Hefei, 230601, Anhui, People’s Republic of China

    Xiongzi Dong

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Tian, Y., Wang, L., Fu, G. et al. Theoretical investigation on the substituent effects of the C–H/π interaction. Theor Chem Acc 139, 78 (2020). https://doi.org/10.1007/s00214-020-02595-y

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