Molecular and Supramolecular Study of Uranium/Plutonium Liquid–Liquid Extraction with N,N‑Dialkylamides

In the context of the separation of uranium and plutonium from spent fuel allowed by N,N-dialkylamides, three regioisomers of N,N-di­(2-ethylhexyl) butyramide (DEHBA or ββ) and the diastereopure isomers of N-(2-ethylhexyl)-N-(oct-3-yl)­butyramide (EHOBA or αβ) were synthesized to assess their extraction performance and to study the mechanisms at the origin of the differences observed between the stereo- and regioisomers. The N,N-dialkylamides showed differences in extraction, with a greater effect of regio- than stereoisomerism. A mechanistic study at both the molecular and supramolecular scales was initially applied to explain these effects. X-ray absorption and UV–vis spectroscopy showed that uranium is extracted by a UO2(NO3)2L2 complex, which is not very sensitive to steric hindrance, while plutonium is extracted by two complexes, Pu­(NO3)4L2 and Pu­(NO3)6(HL)2, which are differently affected by stereo- and regioisomerism. Investigations at the supramolecular scale also showed that Pu­(NO3)4L2 complexes are disadvantaged by the bulkiness of the extractants, while Pu­(NO3)6(HL)2 is favored by the preformation of larger supramolecular aggregates.