Chemical Speciation of Neptunium(VI) under Strongly Alkaline Conditions. Structure, Composition, and Oxo Ligand Exchange

Abstract

Hexavalent neptunium can be solubilized in 0.5-3.5 M aqueous MOH (M = Li(+), Na(+), NMe4(+) = TMA(+)) solutions. Single crystals were obtained from cooling of a dilute solution of Co(NH3)6Cl3 and NpO2(2+) in 3.5 M [N(Me)4]OH to 5 °C. A single-crystal X-ray diffraction study revealed the molecular formula of [Co(NH3)6]2[NpO2(OH)4]3·H2O, isostructural with the uranium analogue. The asymmetric unit contains three distinct NpO2(OH)4(2-) ions, each with pseudooctahedral coordination geometry with trans-oxo ligands. The average Np═O and Np-OH distances were determined to be 1.80(1) and 2.24(1) Å, respectively. EXAFS data and fits at the Np L(III)-edge on solid [Co(NH3)6]2[NpO2(OH)4]3·H2O and aqueous solutions of NpO2(2+) in 2.5 and 3.5 M (TMA)OH revealed bond lengths nearly identical with those determined by X-ray diffraction but with an increase in the number of equatorial ligands with increasing (TMA)OH concentration. Raman spectra of single crystals of [Co(NH3)6]2[NpO2(OH)4]3·H2O reveal a ν1(O═Np═O) symmetric stretch at 741 cm(-1). Raman spectra of NpO2(2+) recorded in a 0.6-2.2 M LiOH solution reveal a single ν1 frequency of 769 cm(-1). Facile exchange of the neptunyl oxo ligands with the water solvent was also observed with Raman spectroscopy performed with (16)O- and (18)O-enriched water solvent. The combination of EXAFS and Raman data suggests that NpO2(OH)4(2-) is the dominant solution species under the conditions of study and that a small amount of a second species, NpO2(OH)5(3-), may also be present at higher alkalinity. Crystal data for [Co(NH3)6]2[NpO2(OH)4]3·H2O: monoclinic, space group C2/c, a = 17.344(4) Å, b = 12.177(3) Å, c = 15.273 Å, β = 120.17(2)°, Z = 4, R1 = 0.0359, wR2 = 0.0729.