The goal of this work is to model the nature of the chemical species [CdCl2(extractant)2] that are formed during the solvent (or liquid-liquid) extraction of the toxic cadmium(II) from chloride-containing aqueous media using hydrophobic 2-pyridyl ketoximes as extractants. Our coordination chemistry approach involves the study of the reactions between cadmium(II) chloride dihydrate and phenyl 2-pyridyl ketoxime (phpaoH) in water-containing acetone. The reactions have provided access to complexes [CdCl2(phpaoH)2]∙H2O (1∙H2O) and {[CdCl2(phpaoH)]}n (2); the solid-state structures of which have been determined by single-crystal X-ray crystallography. In both complexes, phpaoH behaves as an N,N'-bidentate chelating ligand. The complexes have been characterized by solid-state IR and Raman spectra, and by solution 1H NMR spectra. The preparation and characterization of 1∙H2O provide strong evidence for the existence of the species [CdCl2(extractant)2] that have been proposed to be formed during the liquid-liquid extraction process of Cd(II), allowing the efficient transfer of the toxic metal ion from the aqueous phase into the organic phase.
Keywords: 2-pyridyl ketoximes as cadmium(II) extractants; Raman spectra; cadmium(II); coordination chemistry; model studies for liquid-liquid extraction; phenyl 2-pyridyl ketoxime as ligand; single-crystal X-ray structures.