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• W2171503546 abstract "Amide-functionalised salen ligands capable of extracting metal salts have been synthesised and characterised. Single-crystal X-ray structure determinations of complexes of NiSO4, [Ni(L)(SO4)], confirm that the ionophores are in a zwitterionic form with NiII bound in the deprotonated salen moiety and the SO42− ion associated with protonated pendant N′-amidopiperazine groups. Treatment of [Ni(L)(SO4)] with base removes the protons from the pendant amido–amine group resulting in loss of the SO42− ion and formation of metal-only complexes of type [Ni(L−2H)], which have been characterized by single-crystal X-ray diffraction. Three of the ligands with solubilities suitable for solvent extraction studies show loading and stripping pH-profiles that are suitable for the recovery of CuSO4 or CuCl2 from industrial leach solutions. The copper-only complexes, [Cu(L−2H)], are selective for Cl− over SO42− in both solvent extraction and bulk liquid membrane transport experiments and were found to bind Cl− in two steps via the formation of a 1:1:1 [Cu(L−H)Cl] assembly, followed by a 1:1:2 [Cu(L)Cl2] assembly as the pH of the aqueous phase is lowered. The anion transport selectivity was evaluated for a number of other mono-charged anions and interestingly the ligands were found to display a preference for the Br− ion. To probe the influence of the Hofmeister bias on the selectivity of anion complexation, single-phase potentiometric titration experiments were employed to investigate the binding of SO42− and Cl− by one of the copper only complexes, [Cu(L−2H)] in 95 %/5 % MeOH/water. Under these conditions selectivity was reversed (SO42−>Cl−) confirming that the Hofmeister bias, which reflects the relative hydration energies of the anions, dominates the selectivity of anion extraction from aqueous media into CHCl3." @default.
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• W2171503546 date "2007-07-16" @default.
• W2171503546 modified "2023-10-14" @default.
• W2171503546 title "Anion Selectivity in Zwitterionic Amide-Functionalised Metal Salt Extractants" @default.
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• W2171503546 doi "https://doi.org/10.1002/chem.200601874" @default.
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