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Electronic and topological properties of interactions between imidazolium-based ionic liquids and thiophenic compounds: a theoretical investigation

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Abstract

To deepen the understanding the interactions of thiophenic compounds in ionic liquids, we have performed a systemic study on the electronic structures, and topological properties of interactions between N-ethyl-N-ethylimidazolium diethyl phosphate ([EEIM][DEP]) ionic liquid and 3-methylthiophene (3-MT), benzothiophene (BT), or dibenzothiophene (DBT) using density functional theory. From NBO atomic charges and electrostatic potential analyses, most of the positive charge is located on C2–H2 in the [EEIM] cation, and the negative charge is focused on oxygen atoms in [DEP] anion, implying oxygen atoms in [DEP] should easily attack C2–H2 in [EEIM]. The electrostatic interaction between anion and cation may be dominant for the formation of the [EEIM]–[DEP] ion pair. The large stabilizing effect is due to the strong orbital interactions between the antibonding orbital of proton donor σ*(C2–H2) in [EEIM] cation and the lone pairs of proton acceptor LP(O) in [DEP] anion. A common feature of [EEIM][DEP], [EEIM][DEP]-3-MT/BT/DBT complexes is the presence of hydrogen bonds between [EEIM] cation and [DEP] anion. This work has also given the interacting mechanism of 3-MT, BT, and DBT adsorption on [EEIM][DEP] ionic liquid. Both [EEIM] cation and [DEP] anion are shown to play important roles in interactions between 3-MT, BT, DBT and [EEIM][DEP], which has been corroborated by NBO and AIM analyses. The π···π, π···C–H and hydrogen bonding interactions occur between [EEIM][DEP] and 3-MT, BT, DBT. The strength of sulfur involved interactions between 3-MT, BT, DBT and [EEIM][DEP] follows the order of 3-MT > BT > DBT. The order of interaction energies between [EEIM][DEP] and 3-MT, BT, DBT is 3-MT < BT < DBT, in agreement with the order of extractive selectivity from fuel oils (DBT > BT > 3-MT) in terms of sulfur partition coefficients.

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Acknowledgments

The authors gratefully acknowledge financial support from the Natural Science Foundation of China (21176259). Awarded foundation for excellent young and middle-aged scientist of Shandong Province, China (BS2010NJ024) and the Natural Science Foundation of Shandong Province (ZR2011BQ004), China.

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Authors and Affiliations

  1. College of Science, China University of Petroleum (East China), Qingdao, 266580, Shandong, China

    Renqing Lü & Yukun Lu

  2. College of Chemical Engineering, China University of Petroleum (East China), Qingdao, 266580, Shandong, China

    Dong Liu & Jin Lin

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  1. Renqing Lü
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Correspondence to Renqing Lü.

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Lü, R., Liu, D., Lu, Y. et al. Electronic and topological properties of interactions between imidazolium-based ionic liquids and thiophenic compounds: a theoretical investigation. J IRAN CHEM SOC 10, 733–744 (2013). https://doi.org/10.1007/s13738-012-0207-z

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  • DOI: https://doi.org/10.1007/s13738-012-0207-z

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