A DFT study of the affinity of lanthanide and actinide ions for sulfur-donor and nitrogen-donor ligands in aqueous solution

DFT calculations are reported on the affinity of An(III) (An = actinide) and Ln(III) (Ln = lanthanide) ions for ligands with nitrogen-donor and sulfur-donor groups in aqueous solution, aimed at evaluating such donor groups as the basis for separating Am(III) from Ln(III) ions in the processing of nuclear waste. DFT calculations of Delta G(DFT) at 298 K for the gas-phase reactions: [M(H2O)(6)](3+)(g) + L(g) -> M(H2O)(5)L](3+) (g) + H2O(g), where L is NH3 and M is a variety of Ln(III), An(III) ions, and UO22+ and NpO22+ are reported, as well as for the corresponding reactions for the nona-aqua ions for Ln(III) and An(III) ions. Also reported are Delta G(DFT) for the reactions for L = H2S, as representative of thioethers in aqueous solution, for M = Ln(III) and An(III) ions, as well as Al(III), Ga(III), In(III), Tl(III), Bi(III), Fe(III), and Cr(III). Delta G(DFT) for formation of NH3 complexes in the gas-phase correlates well with Delta G(aq) values for formation of the corresponding complexes in aqueous solution. The logK(1)(NH3) values were predicted by the equation: logK(1) = E-a center dot E-b + C-a center dot C-b (R. D. Hancock, A. E. Martell, Chem. Rev. 89 (1989) 1875.), where E and C are empirical parameters representing the tendencies of the acids ('a') and bases ('b') towards ionic and covalent bonding respectively. Correlations involving Delta G(DFT) for the reactions for L = H2S allow for prediction of logK(1)(R2S) for complexes of thioethers (R = CH2CH2OH). The importance of predicted logK(1)(NH3) values lies in the fact that logK(1) for polydentate N-donor ligands correlates with logK(1)(NH3) for a series of metal ions, so that logK(1)(NH3) for any metal ion is an important consideration in ligand design. In the case of saturated N-donor ligands, this is a simple linear relationship, which suggests that saturated N-donors could lead to high Am(III)/Ln(III) selectivities. For ligands that contain pyridyl-type donors, such as 1,10-phenanthroline or terpyridyl, the correlation of logK(1) with logK(1)(NH3) is separated into two linear relations for M(II) and M(III) ions, with M(III) ions having lower affinity for pyridyl donors than do M(II) ions of similar logK(1)(NH3). The low slope of, for example, logK(1)(terpyridyl) versus logK(1)(NH3) for M(III) ions suggests that ligands based only on pyridyl-type donor groups may not be able to produce large Am(III)/Ln(III) selectivities. The calculations on thioether complexes also suggest that such weakly basic S-donors would produce only weak Am(III)/Ln(III) selectivity, but that more strongly basic thiol-type donors might produce larger selectivities. (C) 2012 Elsevier B. V. All rights reserved.