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A B3LYP and MP2(full) theoretical investigation into cooperativity effects, aromaticity and thermodynamic properties in the Na+⋯benzonitrile⋯H2O ternary complex

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Abstract

The cooperativity effects between H-bonding and Na+⋯π or Na+⋯σ interactions in Na+⋯benzonitrile⋯H2O complexes were investigated using the B3LYP and MP2(full) methods with 6-311++G(2d,p) and aug-cc-pVTZ basis sets. The thermodynamic cooperativity and the influence of this cooperativity on aromaticity was evaluated by nucleus-independent chemical shifts (NICS). The results showed that the influence of the Na+⋯σ or Na+⋯π interaction on the hydrogen bond is more pronounced than that of the latter on the former. The cooperativity effect appeared in the Na+⋯σ interaction complex while the anti-cooperativity effect tended to be in the Na+⋯π system. The change in enthalpy is the major factor driving cooperativity. Thermodynamic cooperativity is not in accordance with the cooperativity effect evaluated by the change of interaction energy. The ring aromaticity of is weakened while the bond dissociation energy (BDE) of the C–CN bond increases upon ternary complex formation. The cooperativity effect (E coop) correlates with R c (NICS(1)ternary/NICS(1)binary) and ΔΔδ (Δδ ternary − Δδ binary) involving the ring and C ≡ N bond, as well as R BDE(C–CN) [BDE(C–CN)ternary/BDE(C–CN)binary], respectively. AIM (atoms in molecules) analysis confirms the existence of cooperativity.

Probing the influences of cooperativity on aromaticity and thermodynamic properties

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Authors and Affiliations

  1. College of Chemical Engineering and Environment, North University of China, Taiyuan, 030051, China

    Guang-ming Zhao, Yu-cun Liu, Tao Chai & Fu-de Ren

  2. The Third Hospital of Shanxi Medical University, Taiyuan, 030053, China

    Wen-jing Shi

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  1. Guang-ming Zhao
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Correspondence to Fu-de Ren.

Appendix A. Supplementary data

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894_2014_2341_MOESM1_ESM.doc

Some geometrical parameters of the binary and ternary complexes, and the interaction energies of the binary systems are given in this Appendix. (DOC 2317 kb)

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Zhao, Gm., Liu, Yc., Shi, Wj. et al. A B3LYP and MP2(full) theoretical investigation into cooperativity effects, aromaticity and thermodynamic properties in the Na+⋯benzonitrile⋯H2O ternary complex. J Mol Model 20, 2341 (2014). https://doi.org/10.1007/s00894-014-2341-2

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