Search

The focus of this study is on the relationship between uranyl(vi) poly-peroxo clusters in the solid state and their possible precursors in solution. For this purpose, the complex formation in the ternary U(vi)–H2O2–F− system has been studied by potentiometric titrations, measuring p[H+] and p[F−], revealing that significant amounts of ternary uranyl(vi)–peroxide–fluoride complexes are formed. Based on the analysis of these data we find that there are two models consistent with structure data and previous speciation in the uranyl(vi)–peroxide–carbonate system (Dalton. Trans., 2012, 41, 11635–11641). One model contains ternary complexes (UO2)4(O2)4F− and (UO2)4(O2)4F22− and the other (UO2)4(O2)4F− and (UO2)5(O2)5F33−; we have chosen the second model as the one most consistent with available information. We suggest that (UO2)4(O2)4F− is a building block in the U-24 cluster, [Na6(OH2)8]@[UO2(O2)F]2418− identified in a single-crystal X-ray diffraction study of the solid phase that slowly precipitates from the slightly acidic test solutions. At p[H+] ≈ 9.5, a new solid phase is formed that contains the cluster [Na6(OH2)8]@[UO2(O2)OH]2418−, also identified from an X-ray structure. Both structures contain η2–η2 bridging peroxide and η2 bridging fluoride or hydroxide ions, respectively. As fluoride bridges are unknown in solution coordination chemistry, it is unlikely that the U-24 fluoride cluster is formed in solution. We suggest that both the solid state fluoride and hydroxide clusters are formed in the crystallization from smaller precursors identified in solution. The study illustrates the importance of accurate control of the solution chemistry when preparing poly-peroxo-metallate clusters and also that the mechanism of their formation is still an open field of research. [ABSTRACT FROM AUTHOR]

The protonation reactions of oxalate (ox) and the complex formation of uranium(vi) with oxalate in 1.05 mol kg(-1) NaClO(4) were studied at variable temperatures (10-70 degrees C). Three U(vi)/ox complexes (UO(2)ox(j)((2-2j)+) with j = 1, 2, 3) were identified in this temperature range. The formation constants and the molar enthalpies of complexation were determined by spectrophotometry and calorimetry. The complexation of uranium(vi) with oxalate ion is exothermic at lower temperatures (10-40 degrees C) and becomes endothermic at higher temperatures (55-70 degrees C). In spite of this, the free energy of complexation becomes more negative at higher temperatures due to increasingly more positive entropy of complexation that exceeds the increase of the enthalpy of complexation. The thermodynamic parameters at different temperatures, in conjunction with the literature data for other dicarboxylic acids, provide insight into the relative strength of U(vi) complexes with a series of dicarboxylic acids (oxalic, malonic and oxydiacetic) and rationalization for the highest stability of U(vi)/oxalate complexes in the series. The data reported in this study are of importance in predicting the migration of uranium(vi) in geological environments in the case of failure of the engineering barriers, which protect waste repositories.