On the Aqueous Chemistry of the UIV–DOTA Complex

The 1,4,7,10-tetrazacyclodecane-1,4,7,10-tetraacetic acid (DOTA) aqueous complex of U^IV with H₂O, OH^?, and F^? as axial ligands was studied by using UV/Vis spectrophotometry, ESI-MS, NMR spectroscopy, X-ray crystallography, and electrochemistry. The U^IV–DOTA complex with either water or fluoride as axial ligands was found to be inert to oxidation by molecular oxygen, whereas the complex with hydroxide as an axial ligand slowly hydrolyzed and was oxidized by dioxygen to a diuranate precipitate. The combined data set acquired shows that, although axial substitution of fluoride and hydroxide ligands instead of water does not seem to significantly change the aqueous DOTA complex structure, it has an important effect on the electronic configuration of the complex. The U^IV/U^III redox couple was found to be quasi-reversible for the complex with both axially bonded H₂O and hydroxide, but irreversible for the complex with axially bonded fluoride. Intriguingly, binding of the axial fluoride renders the irreversible one-electron U^V/U^IV oxidation of the U^IV(DOTA)(H₂O)] complex quasi-reversible, which suggests the formation of the short-lived pentavalent form of the complex, an aqueous non-uranyl chelated U^V cation.