title: Thermodynamic study of the complexation of trivalent actinide and lanthanide cations by ADPTZ, a tridentate N-donor ligand.
abstract: To better understand the bonding in complexes of f-elements by polydentate N-donor ligands, the complexation of americium(III) and lanthanide(III) cations by 2-amino-4,6-di-(pyridin-2-yl)-1,3,5-triazine (ADPTZ) was studied using a thermodynamic approach. The stability constants of the 1:1 complexes in a methanol/water mixture (75/25 vol %) were determined by UV-visible spectrophotometry for every lanthanide(III) ion (except promethium), and yttrium(III) and americium(III) cations. The thermodynamic parameters (DeltaH degrees , DeltaS degrees) of complexation were determined from the temperature dependence of the stability constants and by microcalorimetry. The trends of the variations of DeltaG degrees , DeltaH degrees , and DeltaS degrees across the lanthanide series are compared with published results for other tridentate ligands and confirm strongly ionic bonding in the lanthanide-ADPTZ complexes. Comparison of the thermodynamic properties between the Am- and Ln-ADPTZ complexes highlights an increase in stability of the complexes by a factor of 20 in favor of the americium cation. This difference arises from a more exothermic reaction enthalpy in the case of Am, which is correlated with a greater degree of covalency in the americium-nitrogen bonds. Quantum chemistry calculations performed on a series of trivalent actinide and lanthanide-ADPTZ complexes support the experimental results, showing a slightly greater covalence in the actinide-ligand bonds that originates from a charge transfer from the ligand sigma orbitals to the 5f and 6d orbitals of the actinide ion.
authors.affiliation: CEA-Valrhô, DEN/DRCP/SCPS, B.P. 17171, 30207 Bagnols-sur-Cèze Cedex, France. manuel.miguirditchian@cea.fr
authors.forename: Manuel
authors.initials: M
authors.lastname: Miguirditchian
authors.forename: Denis
authors.initials: D
authors.lastname: Guillaneux
authors.forename: Dominique
authors.initials: D
authors.lastname: Guillaumont
authors.forename: Philippe
authors.initials: P
authors.lastname: Moisy
authors.forename: Charles
authors.initials: C
authors.lastname: Madic
authors.forename: Mark P
authors.initials: MP
authors.lastname: Jensen
authors.forename: Kenneth L
authors.initials: KL
authors.lastname: Nash