X-ray Absorption Spectroscopy of Tricarbonatodioxouranate(V), [UO₂(CO₃)₃]⁵^-, in Aqueous Solution

Actinyl ions (AnO(2)(+) and AnO(2)(2+)) are strongly complexed by CO(3)(2)(-) in aqueous solution, and tricarbonato complexes of UO(2)(2+) and NpO(2)(+), in particular, have been widely studied. Cyclic voltammetry shows that, whereas the Np(V)/Np(VI) couple is reversible in aqueous CO(3)(2)(-) solution, the analogous U couple is irreversible, suggesting significant conformational change on one-electron reduction of [UO(2)(CO(3))(3)](4)(-). EXAFS spectroscopy has been used to define the coordination geometry of the reduced species and shows that both axial and equatorial U-O distances increase on reduction, from 1.80 to 1.90 Å and from 2.43 to 2.50 Å, respectively. The basic geometry of the U complex is apparently unchanged by reduction so any conformational change which does occur must be subtle.