A donor–acceptor model of Ln(III) complexation with terdentate nitrogen planar ligands
Résumé
The mechanism of the formation of a complex between several planar terdentate nitrogen ligands and trivalent
lanthanides (Ln$^{3+}$) in mixed MeOH–H$_2$O solutions is studied and a model is proposed for the thermodynamic
properties of the complexation reactions. The objective is not to cover all aspects of complexation between
Ln$^{3+}$ and planar terdendate nitrogen ligands, but rather to provide insight into the factors that govern the
complexation mechanism. It is shown that the complexation of Ln$^{3+}$ in solution with similar ligands does not
follow the classical trends in change of thermodynamic properties across the Ln series, which have long been
known. Ab initio calculations show that the stability of complexes increases with the increasing electron donor
ability of the coordinating central nitrogen atom (N$_c$) of the ligand and the electron acceptor ability of the
coordinating lateral ones (N$_l$). The effect of covalence for the stability of complexes is analysed. The complexes
with high stability are characterised by distinct covalence of the bonds between Ln$^{3+}$ and the lateral
coordinating nitrogen atoms of the ligand. The thermodynamic properties of complexation of Ln$^{3+}$ with
2,6-bis-(pyridin-2-yl)-4-amino-1,3,5-triazine (Adptz) and 2,6-bis-(1,2,4-triazin-yl)-pyridine (Btp) are compared.
The central ring is negatively charged in the Adptz ligand, but positive in Btp. The strong donor–acceptor
interaction and the net covalence result in an enthalpy mechanism of complexation of Ln$^{3+}$ with Adptz. Owing
to the repulsion between the cation and the central nitrogen atom in the [Ln(Btp)]$^{3+}_{solv}$ complexes, the cation is
pushed away from the nitrogen cavity, the Ln–Nc interatomic distances become larger and the electron donor
ability of N$_c$ is weak. Entropy promotes the formation of the [Ln(Btp)]$^{3+}_{solv}$ complex.
Origine : Fichiers éditeurs autorisés sur une archive ouverte