Supramolecular transport of metal amine complexes through liquid membranes by the ionophore lasalocid A

Chia, P. S. K.; Lindoy, Leonard F.; Walker, Glen W.; Everett, Grover W.

doi:10.1351/pac199365030521

“…Details of the cell design have been published previously. 20 For each experiment both the aqueous phases and the organic phase were stirred separately at 10 rpm; the cell was enclosed by a water jacket and thermostatted at 25 • C. The aqueous source phase was buffered (CH 3 CO 2 H-CH 3 CO 2 Na) at pH 4.9 (±0.1) (6.95 mL of 2 M sodium acetate solution and 3.05 mL of 2 M acetic acid made up to 100 mL) and contained an equimolar solution of the nitrate salts of Co(II), Ni(II), Zn(II), Cu(II), Cd(II), Pb(II) and Ag(I), each at a concentration of 1 × 10 −2 M. The chloroform phase contained the ligand at 1 × 10 −3 M. The aqueous receiving phase was buffered (HCO 2 H-HCO 2 Na) at pH 3.0 ± 0.1 (56.6 mL of 1 M formic acid and 10.0 mL of 1 M sodium hydroxide made up to 100 mL). All transport runs were terminated after 24 h and atomic absorption spectroscopy was used to determine the amount of metal ion transported over this period.…”

Section: Membrane Transportmentioning

confidence: 99%

Assembly of a trinuclear metallo-capsule from a tripodal tris(β-diketone) derivative and copper(ii)

Bray

¹

,

Antonioli

²

,

Clegg

³

et al. 2008

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Synthesis of the 2,2 -dipyridylamine derivatives di-2-pyridylaminomethylbenzene 1, 1,2-bis(di-2-pyridylaminomethyl)benzene 2, 1,3-bis(di-2-pyridylaminomethyl)benzene 3, 2,6-bis(di-2-pyridylaminomethyl)pyridine 4, 1,4-bis(di-2-pyridylaminomethyl)benzene 5, and 1,3,5-tris(di-2-pyridylaminomethyl)benzene 6 are reported together with the single-crystal X-ray structures of 2, 3, and 5. Reaction of individual salts of the type AgX (where X = NO 3 − , PF 6 − , ClO 4 − , or BF 4 − ) with the above ligands has led to the isolation of thirteen Ag(I) complexes, nine of which have also been characterised by X-ray diffraction. In part, the inherent flexibility of the respective ligands has resulted in the adoption of a range of coordination arrangements. A series of liquid-liquid (H 2 O/CHCl 3 ) extraction experiments of Ag(I) with varying concentrations of 1-6 in the organic phase have been undertaken, with the counter ion in the aqueous phase being respectively picrate, perchlorate and nitrate. In general, extraction efficiencies for a given ionophore followed the Hofmeister order of picrate > perchlorate > nitrate; in each case the tris-dpa derivative 6 acting as the most efficient extractant of the six systems investigated. Competitive seven-metal bulk membrane transport experiments (H 2 O/CHCl 3 /H 2 O) employing the above ligands as the ionophore in the organic phase and equimolar concentrations of Co(II), Ni(II), Zn(II), Cu(II), Cd(II), Pb(II) and Ag(I) in the aqueous source phase were also undertaken, with transport occurring against a pH gradient. Under the conditions employed 1 and 5 yielded negligible transport of any of the metals present in the source phase while sole transport selectivity for Ag(I) was observed for 2-4 and 6.

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“…Details of the cell design have been reported previously. [40] It was assumed that transport occurs by means of a symport mechanism [36] in which the anion(s) and protons are co-complexed and co-transported. The source phase consisted of 10 mL of a 0.1 m solution of anion(s) at pH 1.8 AE 0.1 except for the transport experiment employing a SO 4 2À /H 2 PO 4 À mixture, which had a pH of 3.3 AE 0.1.…”

Section: General Preparation Of Copper-only Complexesmentioning

confidence: 99%

Anion Selectivity in Zwitterionic Amide‐Functionalised Metal Salt Extractants

Galbraith

¹

,

Wang

²

,

Li

³

et al. 2007

Chemistry A European J

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Amide-functionalised salen ligands capable of extracting metal salts have been synthesised and characterised. Single-crystal X-ray structure determinations of complexes of NiSO4, [Ni(L)(SO4)], confirm that the ionophores are in a zwitterionic form with Ni(II) bound in the deprotonated salen moiety and the SO4(2-) ion associated with protonated pendant N'-amidopiperazine groups. Treatment of [Ni(L)(SO4)] with base removes the protons from the pendant amido-amine group resulting in loss of the SO4(2-) ion and formation of metal-only complexes of type [Ni(L-2H)], which have been characterized by single-crystal X-ray diffraction. Three of the ligands with solubilities suitable for solvent extraction studies show loading and stripping pH-profiles that are suitable for the recovery of CuSO4 or CuCl2 from industrial leach solutions. The copper-only complexes, [Cu(L-2H)], are selective for Cl- over SO4(2-) in both solvent extraction and bulk liquid membrane transport experiments and were found to bind Cl- in two steps via the formation of a 1:1:1 [Cu(L-H)Cl] assembly, followed by a 1:1:2 [Cu(L)Cl2] assembly as the pH of the aqueous phase is lowered. The anion transport selectivity was evaluated for a number of other mono-charged anions and interestingly the ligands were found to display a preference for the Br- ion. To probe the influence of the Hofmeister bias on the selectivity of anion complexation, single-phase potentiometric titration experiments were employed to investigate the binding of SO4(2-) and Cl- by one of the copper only complexes, [Cu(L-2H)] in 95 %/5 % MeOH/water. Under these conditions selectivity was reversed (SO4(2-)>Cl-) confirming that the Hofmeister bias, which reflects the relative hydration energies of the anions, dominates the selectivity of anion extraction from aqueous media into CHCl3.

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“…Details of the cell design have been published previously. 20 For each experiment both the aqueous phases and the organic phase were stirred separately at 10 rpm; the cell was enclosed by a water jacket and thermostatted at 25…”

Section: Membrane Transportmentioning

confidence: 99%

Silver(i) complexation of linked 2,2′-dipyridylamine derivatives. Synthetic, solvent extraction, membrane transport and X-ray structural studies

Antonioli

¹

,

Bray

²

,

Clegg

³

et al. 2006

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Synthesis of the 2,2 -dipyridylamine derivatives di-2-pyridylaminomethylbenzene 1, 1,2-bis(di-2-pyridylaminomethyl)benzene 2, 1,3-bis(di-2-pyridylaminomethyl)benzene 3, 2,6-bis(di-2-pyridylaminomethyl)pyridine 4, 1,4-bis(di-2-pyridylaminomethyl)benzene 5, and 1,3,5-tris(di-2-pyridylaminomethyl)benzene 6 are reported together with the single-crystal X-ray structures of 2, 3, and 5. Reaction of individual salts of the type AgX (where X = NO 3 − , PF 6 − , ClO 4 − , or BF 4 − ) with the above ligands has led to the isolation of thirteen Ag(I) complexes, nine of which have also been characterised by X-ray diffraction. In part, the inherent flexibility of the respective ligands has resulted in the adoption of a range of coordination arrangements. A series of liquid-liquid (H 2 O/CHCl 3 ) extraction experiments of Ag(I) with varying concentrations of 1-6 in the organic phase have been undertaken, with the counter ion in the aqueous phase being respectively picrate, perchlorate and nitrate. In general, extraction efficiencies for a given ionophore followed the Hofmeister order of picrate > perchlorate > nitrate; in each case the tris-dpa derivative 6 acting as the most efficient extractant of the six systems investigated. Competitive seven-metal bulk membrane transport experiments (H 2 O/CHCl 3 /H 2 O) employing the above ligands as the ionophore in the organic phase and equimolar concentrations of Co(II), Ni(II), Zn(II), Cu(II), Cd(II), Pb(II) and Ag(I) in the aqueous source phase were also undertaken, with transport occurring against a pH gradient. Under the conditions employed 1 and 5 yielded negligible transport of any of the metals present in the source phase while sole transport selectivity for Ag(I) was observed for 2-4 and 6.

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Supramolecular transport of metal amine complexes through liquid membranes by the ionophore lasalocid A

Abstract: Abstract

Cited by 44 publications

References 4 publications

Assembly of a trinuclear metallo-capsule from a tripodal tris(β-diketone) derivative and copper(ii)

Assembly of a trinuclear metallo-capsule from a tripodal tris(β-diketone) derivative and copper(ii)

Anion Selectivity in Zwitterionic Amide‐Functionalised Metal Salt Extractants

Silver(i) complexation of linked 2,2′-dipyridylamine derivatives. Synthetic, solvent extraction, membrane transport and X-ray structural studies

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