Host-guest assembly of ligand systems for metal ion complexation. Synergistic solvent extraction of copper(II) and silver(I) by 1,4,8,11-tetrabenzyl-1,4,8,11-tetraazacyclodecane in combination with carboxylic acids.
Host-guest formation between 1,4,8,11-tetrabenzyl-1,4,8,11-tetraazacyclodecane (1) and lipophilic organic carboxylic acids in chloroform has been investigated and the effect of such ligand assembly on the solvent extraction of copper(II) and silver(I) has been probed. NMR titration experiments in the absence of a metal ion confirm the formation of weak 1:1 and 1:2 (macrocycle:carboxylic acid) assemblies in CDCl(3) between 1 and palmitic (hexadecanoic) acid or 4-tert-butylbenzoic acid while difunctional salicylic acid showed a 1 [ratio] 2 interaction that is somewhat stronger. The interaction between the former two acids and the tetra-N-benzylated macrocycle is significantly less than that reported previously for its non-substituted parent, cyclam; a result that likely reflects the presence of the less-basic, more sterically hindered tertiary nitrogens in 1 relative to the secondary nitrogens present in cyclam. Carboxylic acid-containing assemblies of this type have been used as extractants in a series of solvent extraction (water/chloroform) experiments. From both previous observations as well as from entropy considerations, it was anticipated that the use of a host-guest assembly of the above type for metal-ion complexation might contribute to enhanced metal ion binding (and concomitant enhanced metal ion extraction). Such behaviour is postulated to arise from the components of the coordination sphere being, at least in part, assembled for complex formation. In accord with this, the use of the ligand assembly involving palmitic acid/macrocycle 1 was found to lead to enhanced (synergistic) extraction of copper(II) at a metal ion concentration of 10(-3) mol dm(-3) while, for silver(I), synergism was somewhat marginal at this concentration but was clearly apparent under related conditions when the silver concentration was reduced to 10(-4) mol dm(-3). Similar behaviour towards silver was also observed when 4-tert-butylbenzoic acid was substituted for palmitic acid, while the use of salicylic acid resulted in enhanced (synergistic) extraction at both metal ion concentrations.
Host–guest assembly of ligand systems for metal ion complexation; synergistic solvent extraction of copper(II) ions by N3O2-donor macrocycles and carboxylic or phosphinic acids
Host–guest formation between N3O2-donor macrocyclic hosts and lipophilic organic acid guests (that are themselves potential metal-ion ligands/extractants) has been investigated and the implications of formation of such ligand assemblies for the binding of metal ions have been probed. The formation of 2 ∶ 1 (organic acid ∶ macrocycle) assemblies has been demonstrated using NMR titration experiments in deuterochloroform for 4-tert-butylbenzoic, palmitic, phenylphosphinic, diphenylphosphinic and salicylic acids, with evidence for the additional formation of 1 ∶ 1 intermediates in some cases. Molecular adducts of this type have been used in solvent extraction (water/chloroform) experiments to define the effect of assembly formation on metal ion binding. From entropy considerations it was anticipated that the formation of particular host–guest species of the above type might result in enhanced metal ion binding (and hence enhanced metal ion extraction) – a consequence of the fact that the components of the coordination sphere are, at least in part, assembled for complex formation. Using a range of assemblies of the above type, enhanced (synergistic) extraction of Cu(II) ions was confirmed in all cases. Adducts of 1,12,15-triaza-3,4:9,10-dibenzo-5,8-dioxacycloheptadecane and 1,12,15-triaza-3,4:9,10-bis(4′-tert-butylbenzo)-5,8-dioxacycloheptadecane with 4-tert-butylbenzoic acid and salicylic acid have been isolated and their solid-state structures (and 1 ∶ 2 stoichiometries) confirmed by X-ray diffraction.
Tailoring macrocycles for metal ion binding
Abstract