Solution chemistry of uranyl ion with iminodiacetate and oxydiacetate: A combined NMR/EXAFS and potentiometry/calorimetry study

The solution chemistry of uranyl ion with iminodiacetate (IDA) and oxydiacetate (ODA) was investigated using NMR and EXAFS spectroscopies, potentiometry, and calorimetry. From the NMR and EXAFS data and depending on stoichiometry and pH, three types of metal:ligand complex were identified in solution in the pH range 3-7: 1:1 and 1:2 monomers; a 2:2 dimer. From NMR and EXAFS data for the IDA system and previous studies, we propose the three complex types are [UO2(IDA)(H2O)(2)], [UO2(IDA)(2)](2-), and [(UO2)(2)(IDA)(2)(mu-OH)(2)](2-). From EXAFS spectroscopy, similar 1:1, 2:2, and 1:2 complexes are found for the ODA system, although C-13 NMR spectroscopy was not a useful probe in this system. For the 1:1 and 1:2 complexes in solution, EXAFS spectroscopy is ambiguous because the data can be fitted with either a long U-N/O-ether value (ca. 2.9 Angstrom) suggesting 1,7-coordination of the ligand or a U-C interaction at a similar distance, consistent with terminal bidentate coordination. However, the NMR data of the IDA system suggest that 1,7-coordination is the more likely. The stability constants of the three complexes were determined by potentiometric titrations; the log beta values are 9.90 +/- (0.09) (0.08), 16.42 +/- (0.21) (0.14), and 10.80 +/- (0.22) (0.15) for the 1:1, 1:2, and 2:2 uranyl-IDA complexes, respectively, and 5.77 +/- (0.20)(0.360), 7.84 +/- (0.63) (0.28), and 4.29 +/- (0.90) (0.27) for the 1:1, 1:2, and 2:2 ur anyl-ODA complexes, respectively. The thermodynamic constants for the complexes were calculated from calorimetric titrations; the enthalpy changes (kJ mol(-1)) and entropy changes (J K-1 mol(-1)) of complexation for the 1:1, 1:2, and 2:2 complexes respectively are the following. IDA: 12 +/- 2, 230 +/- 8; 8 +/- 2, 151 +/- 9; -33 +/- 3, -283 +/- 11. ODA: 26 +/- 2, 198 +/- 12; 20 +/- 2, 106 +/- 8; -24 +/- 2; -219 +/- 8.