Copper Extractant Strength: The Effect of Substituents in the 3-Position on Hydroxyoxime Performance

The synthesis and study of a systematic series of phenolic oximes have shown that substitution in the 3-position can greatly affect extractive efficacy. Solid state, solution and gas phase analytical techniques, including X-ray crystallography, EPR and IR spectroscopy and collision induced dissociation mass spectrometry have been assessed for their applicability in interpreting the origins of differences in extractant strength. The dominant substituent effect on pH0.5 is the change in ligand pKa, with the more acidic ligands being stronger extractants. The influence of the 3-substituent on the stabilising intracomplex H-bonding of their copper(II) complexes also affects extractant strength. The 3-NO2 substituted ligand shows the lowest pH0.5 value, due to a combination of its low pKa and a stabilising bifurcated H-bond assembly around the copper(II) centre. Appending an aminomethyl group to the 3-position gives a ligand capable of binding a metal and its attendant anion. These metal salt reagents show potential to open up new flowsheets for the processing of high tenor copper feeds.