Probing the selective separation of potassium ion from sodium ion with cyclopentadienyl anion as receptor: a computational study.

A systematic computational study has been carried out using post-Hartree-Fock and density functional theory methods on half sandwich (M-Cp), sandwich (Cp-M-Cp), inversed sandwich (M-Cp-M), and multi-decker chain complexes of alkali metal ions (Na(+), and K(+)). The binding affinity of cyclopentadienyl anion (Cp) with K(+) and Na(+) ions has been studied in half sandwich, sandwich, inversed sandwich, and multi-decker chain complexes. These complexes have been examined in the aqueous phase. The calculated results show that Cp anion can preferentially bind with Na(+) ion over K(+) ion in aqueous phase. The results obtained from DFT calculations have been compared with the crystal structures of Cp-Na and Cp-K complexes. The Bader's atoms in molecule (AIM) analysis were performed to characterize the non-covalent cation-π interactions in the Cp-M complexes. The calculated electron density at cage critical point indicates the strength of the Cp-M complexes. Energy decomposition analysis (EDA) has also been performed to investigate the origins of these interactions. The electrostatic interaction contributes significantly to the total interaction energy in Cp-M complexes. The relative stability difference of cyclopentadienyl anion (Cp) with K(+) and Na(+) ions in aqueous phase can be exploited for the separations from mixture such as sea bittern. The lower stability of K-Cp complex can induce to precipitate the K(+) ions more easily than the corresponding Na(+) ions. Graphical Abstract Potassium ion from sodium ion with cyclopentadienyl anion as receptor.