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Complexation of alkali metal cations by crown-ether type podands with applications in solvent extraction: insights from quantum chemical calculations

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Abstract

The complexation behavior of nine polyether type podands with a varying number of oxygen donor atoms (4–10) towards the alkali metal cations Li+, Na+ and K+ was studied by quantum chemical methods at the DFT-B3LYP level of theory using the all-electron split-valence 6-311++G(d,p) basis set. The optimized structures of the complexes show a regular increase in the mean cation–oxygen distance with the coordination number. OC–CO dihedral angles of the podand arms were also found to increase with the coordination number and with the size of the cation. Maximum values for the number of strong cation–oxygen interactions (effective coordination numbers) were found for each cation (six for Li+, seven for Na+ and eight for K+). The calculated values for thermodynamic parameters relative to the binding of free and solvated cations to the podands allowed the assessment of binding constants in vacuum, in water and in dichloromethane. The estimated cation extraction constants mimic the experimental extraction trends, but their values are much larger than experimental values. Scale factors were determined to correct the values effectively. For each podand the ratios between the calculated extraction constants of Li+ (or Na+) and the corresponding ones for K+ (seen as extraction selectivities) compare acceptably with the corresponding experimental values.

Stereoscopic view of representative structures of a podand and the corresponding K+ complex, highlighting the C-O-C dipole orientations

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Notes

  1. The symbology used in the present work to designate the podands is based on the number of ethylene glycol (eg) units present in each of the two arms, always bonded to the aromatic ring at ortho positions. So, podand b33 has two equal sized arms consisting of chains with three eg units, comprising a total of eight potentially donor oxygen atoms, bonded at ortho positions to the aromatic ring, and podand b06 has one arm consisting of a chain with six eg units and one methoxy group, comprising a total of eight potentially donor oxygen atoms, bonded at ortho positions to the aromatic ring. Thus, to find the number of potentially donor oxygen atoms of podand b”mn” one just has to perform the sum: m + n + 2.

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  1. Departamento de Química e Bioquímica, Faculdade de Ciências da Universidade do Porto, Requimte, Rua do Campo Alegre, 4169-007, Porto, Portugal

    Mário Valente, Sérgio Filipe Sousa, Alexandre L. Magalhães & Cristina Freire

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  1. Mário Valente
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Valente, M., Sousa, S.F., Magalhães, A.L. et al. Complexation of alkali metal cations by crown-ether type podands with applications in solvent extraction: insights from quantum chemical calculations. J Mol Model 17, 3275–3288 (2011). https://doi.org/10.1007/s00894-011-1004-9

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