Alkyl-substituted phenolic pyrazoles such as 4-methyl-2-[5-(n-octyl)-1H-pyrazol-3-yl]phenol (L2H) are shown to function as Cu-extractants, having similar strength and selectivity over Fe(iii) to 5-nonylsalicylaldoxime which is a component of the commercially used ACORGA® solvent extraction reagents. Substitution in the phenol ring of the new extractants has a major effect on their strength, e.g. 2-nitro-4-methyl-6-[5-(2,4,4-trimethylpentyl)-1H-pyrazol-3-yl]phenol (L4H) which has a nitro group ortho to the phenolic hydroxyl group unit and has an extraction distribution coefficient for Cu nearly three orders of magnitude higher than its unsubstituted analogue 4-methyl-6-[5-(2,4,4-trimethylpentyl)-1H-pyrazol-3-yl]phenol (L8H). X-ray structure determinations and density functional theory (DFT) calculations confirm that inter-ligand hydrogen bonding between the pyrazole NH group and the phenolate oxygen atom stabilise the Cu-complexes, giving pseudomacrocyclic structures. Electron-accepting groups ortho to the phenol oxygen atoms buttress the inter-ligand H-bonding, enhancing extractant strength but the effectiveness of this is very dependent on steric factors. The correlation between the calculated energies of formation of copper complexes in the gas phase and the observed strength of comparably substituted reagents in solvent extraction experiments is remarkable. Analysis of the energies of formation suggests that big differences in strength of extractants arise principally from a combination of the effects of the substituents on the ease of deprotonation of the proligands and, for the ortho-substituted ligands, their propensity to buttress inter-ligand hydrogen bonding.

A series of 3-substituted salicylaldoximes has been used to demonstrate the importance of outer-sphere interactions on the efficacy of solvent extractants that are used to produce approximately one-quarter of the world's copper. The distribution coefficient for extraction of copper by 5-tert-butyl-3-X-salicylaldoximes (X = H, Me, (t)Bu, NO(2), Cl, Br, OMe) varies by more than two orders of magnitude. X-ray structure determinations of preorganized free ligand dimers (10 new structures are reported) indicate that substituents with a hydrogen-bond acceptor atom attached to the 3-carbon atom, ortho to the phenolic oxygen, buttress the intermolecular hydrogen bond from the oximic proton. Density functional theory calculations demonstrate that this hydrogen-bond buttressing is maintained in copper(II) complexes and contributes significantly to their relative stabilities in energy-minimized gas-phase structures. A remarkable correlation between the order of the calculated enthalpies of formation of the copper complexes in the gas phase and the observed strength of the ligands as copper solvent extractants is ascribed to the low solvation energies of species in the water-immiscible phase and/or the similarities of the solvation enthalpies of the preorganized ligand dimers and their copper(II) complexes.

Ligand-ligand interactions in the outer coordination sphere make an important contribution to the effects of 3-substituents on the stabilities of anionic Cu(II) salicylaldoximato complexes [CuL(L-H)](-). When substituents contain a different number of bonds the interpretation of CID tandem mass spectrometry must take into account the ability of ions to redistribute energy acquired in collisions within different numbers of vibrational modes.

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, Electron Paramagnetic Resonance (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 stabilizing 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(s). These metal salt reagents show potential to open up new flowsheets for the processing of high tenor copper feeds.La synthese et l’etude d’une serie systematique d’oximes phenoliques ont montre que la substitution en position-3 pouvait grandement affecter l’efficacite d’extraction. On a evalue des techniques analytiques a l’etat solide, en solution et en phase gazeuse, incluant la cristallographie aux rayons X, la resonance paramagnetique electronique (EPR), la spectroscopie IR et la spectrometrie de masse a dissociation induite par collision pour leur applicabilite dans l’interpretation de l’origine des differences de la force de l’agent d’extraction. L’effet dominant du substituant sur le pH0.5 est le changement de pKa du ligand, les ligands les plus acides etant les agents d’extraction les plus forts. L’influence du substituant-3 sur la liaison-H de l’intracomplexe stabilisant de leurs complexes de cuivre(II) affecte egalement la force de l’agent d’extraction. Le ligand au NO2-3 substitue montre la plus basse valeur de pH0.5 en raison d’une combinaison de son faible pKa et de l’assemblee stabilisante d’un lien H bifurque autour du centre du cuivre(II). Adjoindre un groupe aminomethyle a la position-3 donne un ligand capable de lier un metal et son anion(s) auxiliaire. Ces reactifs metal-sel montrent la possibilite d’ouvrir de nouveaux schemas de procede pour le traitement de charges a haute teneur en cuivre.

Novel polynucleating, di- and tri-acidic ligands have been designed to increase the molar and mass transport efficiencies for the recovery of base metals by solvent extraction.

3-Substitution of salicylaldoximes alters their copper(II) binding strengths by buttressing stabilising hydrogen bonding.

Monosulfonyl derivatives of simple 1,2- and 1,3-diamines (R2HN-R-NHSO2R1 = L) have been shown to be easily deprotonated to give neutral 2:1 complexes, [M(L - H)(2)], with Co(II), Ni(II), Cu(II) or Zn(II). The Ni(II) and Cu(II) complexes with deprotonated N-tosyl-1,2-diaminoethane have a planar N4(2-) donor set and a 14-membered pseudo-macrocyclic structure based on head-to-tail S=O...H-N((amine)) bonding between the two bidentate ligands. In the related tetrahedral Zn(II) complex the ends of the mutually perpendicular bidentate N2- units are too far apart to form a cyclic H-bonded system. X-Ray structure determinations on five free ligands provide evidence for extensive inter-molecular H-bonding, which in the case of N-tosyl-1,3-diaminopropane and its N'-tert-butyl derivative involves formation of dimeric 16-membered pseudo-macrocycles. Despite favourable inter-ligand H-bonding in the neutral 2:1 complexes, these ligands are relatively weak extractants, showing >50% loading of Cu(II) in "pH-swing" equilibria, 2L(org)+ M2+ = [M(L - H)2](org)+ 2 H+, only when the pH of the aqueous phase is raised above 4.

Hexadentate tris-salicylaldimine ligands bearing ortho-N-dialkylaminomethyl substituents have been shown to function as ditopic ligands for NiSO4 or NiCl2. The incorporation of the Ni-ion into the N3O33- site templates the pendant alkylammonium groups to allow them to hydrogen bond to the attendant anion(s). Formulation as complexes of the trianionic/tricationic ligand is supported by X-ray structure determinations of solvated forms of the complexes [Ni(L)SO4] and [Ni(L)Cl]Cl, where L = tris-1,1,1-{2-hydroxy-3-(piperidin-1-ylmethyl)-5-tert-butyl-benzaldiminomethyl} ethane. The kerosene-soluble ligand, tris-2,2',2"-{2-hydroxy-3-(di-n-hexylaminomethyl)-5-nonylbenzaldiminomethyl} amine, functions as a good extractant for nickel salts, showing high selectivity for recovery of NiCl2 over NiSO4. This reagent can be stripped and recycled directly using aqueous ammonia or by first displacing the Ni2+ with acid and then neutralising the pendant alkylammonium groups. The acid-stripping is accompanied by hydrolytic degradation of the reagent, but in many other respects this novel class of reagent shows promise in opening up novel flowsheets for nickel recovery, based on transport of the metal salt as opposed to ion-exchange based processes.