Selective Complexation and Separation of Uranium(VI) from Thorium(IV) with New Tetradentate N,O-Hybrid Diamide Ligands: Synthesis, Extraction, Spectroscopy, and Crystallographic Studies

An unmet challenge in the thorium-uranium fuel cycle is the efficient separation of uranium from thorium. Herein, two new tetradentate N,O-hybrid ligands, N,N'-diethyl-N,N'-di-p-tolyl-2,2'-bipyridine-6,6'-dicarboxamide (Et-Tol-BPDA) and N,N'-diethyl-N,N'-di-p-tolyl-2,2'-bipyrimidine-4,4'-dicarboxamide (Et-Tol-BPymDA), comprising a bipyridine or bipyrimidine core and amide moieties were designed and synthesized for selectively complexing and separating U(VI) from Th(IV). The high U(VI)/Th(IV) extraction selectivity was achieved by Et-Tol-BPDA (SFU/Th = 33 at 3 M HNO3) and Et-Tol-BPymDA (SFU/Th = 73 at 3 M HNO3) in nitric acid solutions. The extraction process for U(VI) or Th(IV) with these two ligands primarily proceeded through the solvation mechanism, as evidenced by slope analyses. Thermodynamic studies for the extraction of U(VI) and Th(IV) revealed a spontaneous process. Results from UV-vis spectroscopic titration and slope analyses demonstrated that U(VI) and Th(IV) each form a 1:1 complex with the two ligands both in the monophasic organic solution and the biphasic extraction system. The stability constants of the 1:1 complexes of Et-Tol-BPDA or Et-Tol-BPymDA with U(VI) were found to be larger than those with Th(IV), which coincide well with the high U(VI)/Th(IV) extraction selectivity. The solid-state structures of Et-Tol-BPDA, Et-Tol-BPymDA, and 1:1 complexes of the two ligands with U(VI) or Th(IV) were analyzed by X-ray diffraction technique. The results from this work implicate the potential of bipyridine- and bipyrimidine-derived diamide ligands for uranium/thorium separation.