Do perchlorate and triflate anions bind to the uranyl cation in an acidic aqueous medium? A combined EXAFS and quantum mechanical investigation.

Structural properties of uranyl cations in acidic aqueous perchlorate and triflate solutions were investigated using uranium LIII -edge extended X-ray absorption fine-structure spectroscopy (EXAFS) in conjunction with quantum mechanical calculations of gas-phase model complexes. EXAFS spectra were measured in aqueous solutions of up to 10 M triflic and 11.5 M perchloric acid, as well as mixtures of perchloric acid and sodium perchlorate. In no case is the perchlorate anion coordinated to UO2(2+). The number of equatorial water molecules bound to UO2(2+) is always about five. In the case of the 10 M CF3SO3H solution, an inner-sphere complexation of the triflate is observed with a U-S radial distance of 3.62 Å. These results are in qualitative agreement with quantum mechanical calculations of model uranyl complexes, according to which the interaction energies of anions follow the order perchlorate