Theoretical studies were carried out on two pairs of americium and europium complexes formed by tetra-N-dentate lipophilic BTBP ligands, neutral [ML(NO(3))(3)] and cationic [ML(2)](3+) where M = Am(III) or Eu(III), and L = 6,6'-bis-(5,6-diethyl-1,2,4-triazin-3-yl)-2,2'-bipyridine (C2-BTBP). Molecular structures of the complexes have been optimized at the B3LYP/6-31G(d) level and total energies of the complexes in various media were estimated using single point calculations performed at the B3LYP/6-311G(d,p) and MP2/6-311G(d,p) levels of theory. In the calculations americium and europium ions were treated using pseudo-relativistic Stuttgart-Dresden effective core potentials and the accompanying basis sets. Selectivity in solvent extraction separation of two metal ions is a co-operative function of contributions from all extractable metal complexes, which depend on physico-chemical properties of each individual complex and on its relative amount in the system. Semi-quantitative analysis of BTBP selectivity in the Am/Eu separation process, based on the contributions from the two pairs of Am(III) and Eu(III) complexes, has been carried out. To calculate the energy of Am/Eu separation, a model of the extraction process was used, consisting of complex formation in water and transfer of the formed complex to the organic phase. Under the assumptions discussed in the paper, this simple two-step model results in reliable values of the calculated differences in the energy changes for each pair of the Am/Eu complexes in both steps of the process. The greater thermodynamic stability (in water) of the Am-BTBP complexes, as compared with the analogous Eu species, caused by greater covalency of the Am-N than Eu-N bonds, is most likely the main reason for BTBP selectivity in the separation of the two metal ions. The other potential reason, i.e. differences in lipophilic properties of the analogous complexes of Am and Eu, is less important with regard to this selectivity.

Theoretical calculations (density functional theory with the scalar relativistic ZORA Hamiltonian) have been performed to obtain the energy and Gibbs free energy of formation of cationic 1 : 3 complexes of americium(iii) and europium(iii) with a tri-O-dentate diglycolamide ligand TEDGA (a model of TODGA extractant), as well as the free energy of their partition between water and an organic diluent. The distribution of electron density over the atoms, bonds, and molecular orbitals was analyzed by means of Mulliken population analysis, the localization procedure of natural bond orbitals, and the Quantum Theory of Atoms-in-Molecules. The stabilities of both [M(TEDGA)(3)](3+) complexes are similar to each other. On the other hand, our recent data for a similar pair of cationic Am/Eu complexes with a softer (HSAB) tetra-N-dentate ligand C2-BTBP show that the [Am(C2-BTBP)(2)](3+) complex is significantly more stable in aqueous solution than its Eu counterpart. The decisive factor stabilizing the Am(3+) complexes over their Eu(3+) analogues is the charge transfer from the ligands, somewhat greater on the 6d(Am(III)) than on 5d(Eu(III)) orbitals. The covalency of M-N bonds in the [M(C2-BTBP)(2)](3+) complexes is greater than that of M-O bonds in [M(TEDGA)(3)](3+), but the latter is not negligible, in particular in the bonds with the oxygen atoms of the amide groups in TEDGA. The analysis of charge distribution over the whole molecules of the complexes shows that the TEDGA molecule is not hard as expected, but a relatively soft Lewis base, only slightly harder than BTBP. This conclusion has been confirmed by the calculation of the chemical hardness of the ligands. Moreover, the comparison of the results of bonding analysis with the calculated energies of complex formation in water and in the gas phase allows us to conclude that the population analysis, QTAIM topological parameters, and SOPT stabilization energy, as well as Wiberg and overlap-weighted NAO indices are the tools for analyzing the covalency rather than the total bond strength.

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1:1 and 1:2 complexes of americium(III) with a hydrophilic anionic SO3–Ph–BTP4− ligand were detected in acidic aqueous nitrate solutions by a solvent extraction method. The determined conditional stability constants of these complexes, logβ1 = 4.35 ± 0.07 and logβ2 = 7.67 ± 0.06, related to 1 M aqueous solutions, are much lower than the literature values for the analogous curium species, determined by TRLFS in very dilute aqueous solutions. There is also no evidence for the existence of the 1:3 Am3+ complex similar to the reported curium(III) complex. A hypothesis has been formulated to explain these discrepancies. It suggests the necessity to carefully check the equilibria in each phase of solvent extraction systems containing two competing ligands—lipophilic and hydrophilic.

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