Cation and anion selectivity of zwitterionic salicylaldoxime metal salt extractants.

Ross S Forgan, James E Davidson, Francesca P A Fabbiani, Stuart G Galbraith, David K Henderson, Stephen A Moggach, Simon Parsons, Peter A Tasker, Fraser J White

Index: Dalton Trans. 39(7) , 1763-70, (2010)

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Abstract

3-Dialkylaminomethyl substituted salicylaldoximes are efficient metal salt extractants, and, in contrast to related "salen"-based reagents, are sufficiently stable to acid hydrolysis to allow commercial application in base metal recovery. Crystal structures show that metal salts are bound by a zwitterionic form of the reagents, with copper(II) nitrate, tetrafluoroborate and trifluoroacetate forming [Cu()(2)X(2)] assemblies in a tritopic arrangement with a trans-disposition of the anions outwith the coordination sphere. Copper(II) chloride, bromide and zinc(II) chloride form 1:1 assemblies, [Cu()X(2)], with the halides in the inner coordination sphere of the metal, leading to high chloride selectivity and very good mass transport efficiencies of CuCl(2). Introduction of the anion-binding sites into the salicylaldoxime extractants changes their cation selectivities; the ligands co-extract small amounts of Fe(III) along with Cu(II) from mixed metal aqueous feed solutions, an issue which will need to be addressed prior to industrial application.