Journal
DALTON TRANSACTIONS
Volume 44, Issue 28, Pages 12771-12779Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5dt01691f
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A new class of conformationally constrained 7-oxabicyclo[2.2.1] heptane-2,3-dicarboxamides (OBDA) of three secondary amines was synthesized, and their extraction behavior for trivalent and tetravalent actinides in HNO3 medium was studied. Amongst the diamides, N, N-bis-2-ethylhexyl substituted diamide showed the best results for actinide extraction. This diamide also exhibited a very low level of extraction for Sr(II) and Ru(III) which is desirable, thus providing higher selectivity for actinides. The stripping of extracted metal ions was achieved using 0.1 M oxalic acid for Pu(IV) or pH similar to 2 solution for Am(III). Third phase formation was not observed for the OBDA ligand even for a higher concentration of Eu up to 5 g L-1 with retention of good D-Eu. The tridentate nature of the OBDA ligand was ascertained by studying the IR and NMR spectra of the Eu(III) complex with the ligand. The OBDA showed the formation of a mixture of mono-and di-solvated species of Eu(III) as indicated by the slope analysis method and ESI-MS. Density functional theoretical (DFT) study was carried out to determine the energy optimized structure of the free ligand and its Am3+ complex.
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