David K. Henderson

Inter-ligand reactions: in situ formation of new polydentate ligands

Two ligands have been synthesized by derivatisation of cyanuric chloride: 6-(diethylamino)-2,4-disulfanyl-1,3,5-triazine (H2SSta) 1 and 6-(diethylamino)-2-hydroxo-4-sulfanyl-1,3,5-triazine (H2OSta) 2 have been characterised by X-ray crystallography, which shows intermolecular hydrogen bonding in the solid state, leading to dimers of 1 and ribbons of 2. On reaction with metal salts both ligands undergo oligomerisation reactions. Compound 1 reacts with nickel chloride to form a mononuclear complex, [Ni{(Sta)S(S2ta)}] 3. In 3 two triazine ligands have reacted, to form a tetradentate ligand in which two triazine rings are bridged by a sulfur group, with a co-ordinated disulfide group present on one ring and a co-ordinated thiolate on the second. Compound 2 reacts with cobalt(II) chloride to form a cage complex, [Co6NaO(OStaH)7{S(Ota)2}2(O2CPh)2(H2O)2] 4. This complicated structure contains two polydentate ligands formed by linking triazine groups through a bridging sulfur. The cage contains four cobalt(II) and two cobalt(III) sites which are assigned by bond length considerations. The compound [Co(OSta)3] 5 co-crystallises with 4, and its structure has also been determined.

Effect of pressure on the crystal structure of salicylaldoxime‐I, and the structure of salicylaldoxime‐II at 5.93 GPa

The effect of pressure on the crystal structure of salicylaldoxime has been investigated. The ambient-pressure phase (salicylaldoxime-I) consists of pairs of molecules interacting through oximic OH...O hydrogen bonds; taken with phenolic OH...N intramolecular hydrogen bonds, these dimers form a pseudo-macrocycle bounded by an R4 4(10) motif. The dimers interact principally via pi...pi stacking contacts. Salicylaldoxime derivatives are used industrially as selective solvent extractants for copper; the selectivity reflects the compatibility of the metal ion with the pseudo-macrocycle cavity size. On increasing the pressure to 5.28 GPa the size of the cavity was found to decrease by an amount comparable to the difference in hole sizes in the structures of the Cu2+ salicylaldoximato complex and its Ni2+ equivalent. On increasing the pressure to 5.93 GPa a new polymorph, salicylaldoxime-II, was obtained in a single-crystal to single-crystal phase transition. PIXEL calculations show that the phase transition is driven in part by relief of intermolecular repulsions in the dimer-forming OH...O-bonded ring motif, and the ten-centre hydrogen-bonding ring motif of the phase I structure is replaced in phase II by a six-centre ring formed by oximic OH...N hydrogen bonds. The transition also relieves repulsions in the pi...pi stacking contacts. The intramolecular OH...N hydrogen bond of phase I is replaced in phase II by a intermolecular phenolic OH...O hydrogen bond, but the total interaction energy of the pairs of molecules connected by this new contact is very slightly repulsive because the electrostatic hydrogen-bond energy is cancelled by the repulsion term. The intra- to intermolecular hydrogen-bond conversion simply promotes efficient packing rather than contributing to the overall lattice energy.

Using the outer coordination sphere to tune the strength of metal extractants.

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 worlds 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.

Transport of metal salts by zwitterionic ligands; simple but highly efficient salicylaldoxime extractants

Attaching dialkylaminomethyl arms to commercial phenolic oxime copper extractants yields reagents which transport base metal salts very efficiently by forming neutral 1:1 or 1:2 complexes with zwitterionic forms of the ligands.

Polyacidic multiloading metal extractants

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.

Structural, magnetic, and electronic properties of phenolic oxime complexes of Cu and Ni.

Square planar complexes of the type Ni(L(1))(2), Ni(L(2))(2), Cu(L(1))(2), and Cu(L(2))(2), where L(1)H = 2-hydroxy-5-t-octylacetophenone oxime and L(2)H = 2-hydroxy-5-n-propylacetophenone oxime, have been prepared and characterized by single-crystal X-ray diffraction, cyclic voltammetry, UV/vis spectroscopy, field-effect-transistor measurements, density functional theory (DFT) and time-dependent DFT (TDDFT) calculations, and, in the case of the paramagnetic species, electron paramagnetic resonance (EPR) and magnetic susceptibility. Variation of alkyl groups on the ligand from t-octyl to n-propyl enabled electronic isolation of the complexes in the crystal structures of M(L(1))(2) contrasting with π-stacking interactions for M(L(2))(2) (M = Ni, Cu). This was evidenced by a one-dimensional antiferromagnetic chain for Cu(L(2))(2) but ideal paramagnetic behavior for Cu(L(1))(2) down to 1.8 K. Despite isostructural single crystal structures for M(L(2))(2), thin-film X-ray diffraction and scanning electron microscopy (SEM) revealed different morphologies depending on the metal and the deposition method (vapor or solution). The Cu complexes displayed limited electronic interaction between the central metal and the delocalized ligands, with more mixing in the case of Ni(II), as shown by electrochemistry and UV/vis spectroscopy. The complexes M(L(2))(2) showed poor charge transport in a field-effect transistor (FET) device despite the ability to form π-stacking structures, and this provides design insights for metal complexes to be used in conductive thin-film devices.

A dual host approach to NiSO4extraction

This paper reports the synthesis of sulphate extractants, N,N′-bis-(2-dibutylamino-ethyl)-isophthalamide (1), pyridine-2,6-dicarboxylic acid bis-[(2-dibutylamino-ethyl)-amide] (2) and 3,4-diphenyl-1H-pyrrole-2,5-dicarboxylic acid bis-[(2-dibutylamino-ethyl)-amide] (3), and demonstrates that, in combination with a commercially available oxime extractant 2-hydroxy-5-nonyl benzaldehyde oxime (P50), these dual host systems are better extractants for nickel(II) sulphate than the metal salt extractant, 5-nonyl-3-dihexylaminomethyl-2-hydroxy-benzaldehyde oxime (4).

Synthesis, structure and magnetic properties of [Cu4(Hmbpp)2(H2NC(O)NH2)2(H2O)8]·4H2O

[Cu4(Hmbpp)2(H2NC(O)NH2)2(H2O)8]·4H2O 1, the first example of a discrete polynuclear copper phosphonate complex isolated from aqueous media was synthesised by the addition of urea to a solution of a copper(II) salt and the bisphosphonic acid ligand 4-methyl-2,6-bis(phosphonomethyl)phenol (H5mbpp). 1 contains four distorted square pyramidal copper atoms and the Cu4 units are linked by a complicated hydrogen bonded network involving co-crystallised water molecules.

Exploiting supramolecular chemistry in metal recovery: novel zwitterionic extractants for nickel(ii) saltsBased on the presentation given at Dalton Discussion No. 5, 10?12th April 2003, Noordwijkerhout, The Netherlands.

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-butylbenzaldiminomethyl}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.

Supramolecular chemistry in metal recovery; H-bond buttressing to tune extractant strength

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