Inorganic Chemistry, Vol.59, No.16, 11459-11468, 2020
Quantitative Precipitation of Uranyl or Plutonyl Nitrate with N-(1-Adamantyl)acetamide in Nitric Acid Aqueous Solution
The reactivity of the N-(1-adamantyl)acetamide ligand (L = adam) has been evaluated as precipitating agent for the hexavalent uranyl cation ([U] = 20-60 g L-1) in concentrated nitric acid aqueous solution (0.5-5 M). It results in the formation of a crystalline complex (UO2)(adam)(2)(NO3)(2)center dot 2(adam) (1), in which the uranyl center is 8-fold coordinated to two chelating nitrate groups and two N-(1-adamantyl)acetamide (= adam) ligands through the oxygen atom of the amide function. Two other noncoordinating adam moieties are also observed in the crystal structure packing and interact through a hydrogen-bond scheme with the uranyl-centered species. A similar molecular assembly has been obtained with the plutonyl(VI) cation, in the complex (PuO2)(adam)(2)(NO3)(2)center dot 2(adam) (2). Precipitation studies indicate high (UO2)(adam)(2)(NO3)(2)center dot 2(adam) formation yields (up to 99%(U) for an L/U molecular ratio of 5/1) for HNO3 concentration in the 0.5-5 M range. However, the precipitation kinetics is rather slow and the reaction is completed after several hours (3-4 h). The calcination of the resulting solid under an air atmosphere led to the formation of the U3O8 oxide from 400 degrees C through a transient phase UO2 fluorite-type (from 200 degrees C).