Summary
Hartree-Fock calculations with the 6–31G* basis have been performed to investigate the structure and Li+ binding energies of the complexes between Li+ and pyridine, diazines, triazines and tetrazines. Structures have been fully optimized at the 3–21G level. As for azole-Li+ and methyldiazole-Li+ complexes, a topological analysis of the Laplacian of the electronic charge density reveals that the azine-Li+ is a typical closed-shell interaction and that the stabilization of the complex is mainly electrostatic. BSSE is quite significant, specially for Li+-bridging complexes. The correlation between calculated Li+ binding energies and proton affinities follows two different linear relationships, one for those cases where Li+ is singly coordinated and a different one for those cases in which an additional three-membered ring is formed. The enhanced stability of these particular conformations explains why while polyazines are less basic than pyridine when the reference acid is a proton; pyridazine and 1,2,4 triazine are more basic than pyridine when the reference acid is Li+. The effect on Li+ binding energies of systematic nitrogen substitution roughly follows an additive model.
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Alcamí, M., Mó, O., de Paz, J.J.G. et al. Enhanced Li+ binding energies of some azines: a molecular orbital study. Theoret. Chim. Acta 77, 1–15 (1990). https://doi.org/10.1007/BF01114648
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DOI: https://doi.org/10.1007/BF01114648