caa a22 4500 465818455 CHVBK 20180323112129.0 cr unu---uuuuu 170327e19900101xx s 000 0 eng 10.1007/BF01114648 doi (NATIONALLICENCE)springer-10.1007/BF01114648 Enhanced Li+ binding energies of some azines: a molecular orbital study [Elektronische Daten] [Manuel Alcamí, Otilia Mó, José de Paz, Manuel Yáñez] 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. Springer-Verlag, 1990 Azines nationallicence Li+ binding energies nationallicence Intrinsic basicities nationallicence Alcamí Manuel Departamento de Química, C-XIV, Facultad de Ciencias, Universidad Autónoma de Madrid, Canto Blanco, E-28049, Madrid, Spain aut Mó Otilia Departamento de Química, C-XIV, Facultad de Ciencias, Universidad Autónoma de Madrid, Canto Blanco, E-28049, Madrid, Spain aut de Paz José Departamento de Química, C-XIV, Facultad de Ciencias, Universidad Autónoma de Madrid, Canto Blanco, E-28049, Madrid, Spain aut Yáñez Manuel Departamento de Química, C-XIV, Facultad de Ciencias, Universidad Autónoma de Madrid, Canto Blanco, E-28049, Madrid, Spain aut Theoretica chimica acta Springer-Verlag 77/1(1990-01-01), 1-15 0040-5744 77:1<1 1990 77 214 https://doi.org/10.1007/BF01114648 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/BF01114648 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Alcamí Manuel Departamento de Química, C-XIV, Facultad de Ciencias, Universidad Autónoma de Madrid, Canto Blanco, E-28049, Madrid, Spain aut NATIONALLICENCE 700 1- Mó Otilia Departamento de Química, C-XIV, Facultad de Ciencias, Universidad Autónoma de Madrid, Canto Blanco, E-28049, Madrid, Spain aut NATIONALLICENCE 700 1- de Paz José Departamento de Química, C-XIV, Facultad de Ciencias, Universidad Autónoma de Madrid, Canto Blanco, E-28049, Madrid, Spain aut NATIONALLICENCE 700 1- Yáñez Manuel Departamento de Química, C-XIV, Facultad de Ciencias, Universidad Autónoma de Madrid, Canto Blanco, E-28049, Madrid, Spain aut NATIONALLICENCE 773 0- Theoretica chimica acta Springer-Verlag 77/1(1990-01-01), 1-15 0040-5744 77:1<1 1990 77 214 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer