Dimeric and Trimeric Uranyl(VI)-Citrate Complexes in Aqueous Solution.

This research addresses a subject discussed controversially for almost 70 years. The interactions between the uranyl(VI) ion, U(VI), and citric acid, H3Cit, were examined using a multi-method approach comprising nuclear magnetic resonance (NMR), ultraviolet-visible (UV-vis), attenuated total reflectance Fourier-transform infrared (ATR FT-IR), and extended X-ray absorption fine-structure (EXAFS) spectroscopies as well as density functional theory (DFT) calculations. Combining 17O NMR spectroscopy and DFT calculation provided an unambiguous decision on complex configurations, evidencing for the first time that the dimeric complex, (UO2)2(HCit-H)22-, exists as two diastereomers with the syn-isomer in aqueous solution strongly favored over the anti-isomer. Both isomers interconvert mutually with exchange rates of ∼30 s-1 at -6 °C and ∼249 s-1 at 60 °C in acidic solution corresponding to an activation barrier of about 24 kJ mol-1. Upon increasing the pH value, ternary dimeric mono- and bis-hydroxo as well as trimeric complexes form, that is, (UO2)2(HCit-H)2(OH)3-, (UO2)2(HCit-H)2(OH)24-, (UO2)3(O)(Cit-H)38-, and (UO2)3(O)(OH)(Cit-H)25-, respectively. Stability constants were determined for all dimeric and trimeric species, with log ß° = -(8.6 ± 0.2) for the 3:3 species being unprecedented. Additionally, in the 6:6 sandwich complex, formed from two units of 3:3 species, the 17O NMR resonance of the trinuclear uranyl(VI) core bridging µ3-O is shown for the first time. Species distribution calculations suggest that the characterized polynuclear U(VI)-citrate species do not significantly increase uranium(VI) mobility in the environment. Furthermore, we revise the misconceptions in the aqueous U(VI)-citric acid solution chemistry, that is, structures proposed and repeatedly taken up, and outline generalized isostructural considerations to provide a basis for future U(VI) complexation studies.

Aqueous uranium(VI) complexes with acetic and succinic acid: speciation and structure revisited.

We employed density functional theory (DFT) calculations, and ultraviolet-visible (UV-vis), extended X-ray absorption fine-structure (EXAFS), and attenuated total reflection Fourier-transform infrared (IR) spectroscopy analyzed with iterative transformation factor analysis (ITFA) to determine the structures and the pH-speciation of aqueous acetate (ac) and succinate (suc) U(VI) complexes. In the acetate system, all spectroscopies confirm the thermodynamically predicted pH-speciation by Ahrland (1951), with the hydrated uranyl ion and a 1:1, a 1:2 and a 1:3 U(VI)-ac complex. In the succinate system, we identified a new 1:3 U(VI)-suc complex, in addition to the previously known 1:1 and 1:2 U(VI)-suc complexes, and determined the pH-speciation for all complexes. The IR spectra show absorption bands of the antisymmetric stretching mode of the uranyl mojety (υ3(UO2)) at 949, 939, 924 cm(-1) and at 950, 938, 925 cm(-1) for the 1:1, 1:2 and 1:3 U(VI)-ac and U(VI)-suc complexes, respectively. IR absorption bands at 1535 and 1534 cm(-1) and at 1465 and 1462 cm(-1) are assigned to the antisymmetric υ3,as(COO) and symmetric υ3,s(COO) stretching mode of bidentately coordinated carboxylic groups in the U(VI)-ac and U(VI)-suc complexes. The assignment of the three IR bands (υ3(UO2), υ3,as(COO), υ3,s(COO)) and the stoichiometry of the complexes is supported by DFT calculations. The UV-vis spectra of the equivalent U(VI)-ac and U(VI)-suc complexes are similar suggesting common structural features. Consistent with IR spectroscopy and DFT calculations, EXAFS showed a bidentate coordination of the carboxylic groups to the equatorial plane of the uranyl moiety for all uranyl ligand complexes except for the newly detected 1:3 U(VI)-suc complex, where two carboxylic groups coordinate bidentately and one carboxylic group coordinates monodentately. All 1:1 and 1:2 complexes have a U-Owater distance of ∼2.36 Å, which is shorter than the U-Owater distance of ∼2.40 Å of the hydrated uranyl ion. For all complexes the U-Ocarboxyl distance of the bidentately coordinated carboxylic group is ∼2.47 Å, while the monodentately coordinated carboxylic group of the 1:3 U(VI)-suc complex has a U-Ocarboxyl distance of ∼2.36 Å, that is, similar to the short U-Owater distance in the 1:1 and 1:2 complexes.

Formic acid interaction with the uranyl(VI) ion: structural and photochemical characterization.

Complex formation between the uranyl(VI) ion and formic acid was studied by infrared absorption (IR) and X-ray absorption (EXAFS) spectroscopy as well as density functional theory (DFT) calculations. In contrast to the acetate ion which forms exclusively a bidentate complex with uranyl(VI), the formate ion binds to uranyl(VI) in a unidentate fashion. The photochemistry of the uranyl(VI)-formic acid system was explored by DFT calculations and photoreduction of uranyl(VI) in the presence of formic acid was found to occur via an intermolecular process, that is, hydrogen abstraction from hydrogenformate by the photo-excited uranyl(VI). There is no photo-induced decarboxylation of uranyl(VI) formate via an intramolecular process, presumably due to lack of a C=C double bond.