Unique selectivity reversal between Am³⁺ and Eu³⁺ ions by incorporation of alkyl branching in diglycolamide derivatives: DFT validation of experimental results

Abstract

Two diglycolamide (DGA) derivatives having n-butyl (nBuDGA) and s-butyl (sBuDGA) groups have been used for the extraction of Am3+ and Eu3+ to study the role of alkyl chain branching on...

Remarkable Improvement in Am3+ and Cm3+ Separation Using a Cooperative Counter Selectivity Strategy by a Combination of Branched Diglycolamides and Hydrophilic Polyaza-heterocycles

“…In the case of TiBDGA, where the branching is at the β-carbon, the metal–ligand stoichiometries reduced to 2 in the case of both metal ions (Figure ), indicating that the metal–ligand interactions become weaker in the case of TiBDGA, resulting in a lower metal–ligand stoichiometry in the extracted complex. Formation of lower stoichiometric complexes during the extraction by DGA derivatives with branching at the α- or β-carbon atom is well reported in the literature. , Because of the lower lipophilicity of the lower stoichiometric complexes, these branched DGA derivatives show lower extraction compared to the DGA derivatives having straight alkyl chains or branching away from the amidic N atoms.…”

“…Formation of lower stoichiometric complexes during the extraction by DGA derivatives with branching at the αor β-carbon atom is well reported in the literature. 50,51 Because of the lower lipophilicity of the lower stoichiometric complexes, these branched DGA derivatives show lower extraction compared to the DGA derivatives having straight alkyl chains or branching away from the amidic N atoms. Extraction studies of both metal ions by TiBDGA and TiPDGA were also carried out by varying the SO 3 PhBTPhen concentration, the slope values being ∼1 in all cases (Figure S2).…”

Ligand structure and diluent nature in defining improved Am3+ and Cm3+ separation using diglycolamides: a combined solvent extraction and DFT study

“…N , N , N ′, N ′-tetra ( sec -butyl) diglycolamide (TsBDGA), decreases monotonically along the lanthanide series. 22 Branched alkyl DGA ligands in combination with the suphonated BTP ligand in the aqueous phase are expected to show selective extraction of Am 3+ over Cm 3+ . The insolubility of TsBDGA in the n -dodecane medium forced us to choose an alternative branched alkyl DGA derivative for the selective Am 3+ extraction.…”