Competitive bulk liquid membrane transport of some metal ions using RC(S)NHP(S)(OiPr)2 as ionophores. Unusual supramolecular “honeycomb” aggregate of the polynuclear copper(I) complex of H2NC(S)NHP(S)(OiPr)2CCDC reference number 706436. For crystallographic data in CIF or other electronic format see DOI: 10.1039/b904114a

Abstract

Competitive transport experiments involving metal ions from an aqueous source phase through a chloroform membrane into an aqueous receiving phase have been carried out using a series of N-(thio)phosphorylated (thio)amide and thiourea ligands as ionophores in the organic phase. The source phase contained equimolar concentrations of Co^II, Ni^II, Cu^II, Zn^II, Ag^I, Cd^II and Pb^II with the source and receiving phases being buffered at different pH. Good transport properties were observed for Ag^I in the case of HL¹³. The best extraction properties have been shown by H₃L¹, H₃L⁸, H₂L⁷, H₃L⁹ and H₃L¹¹ which contain an unsubstituted nitrogen atom at the CS groups (H₃L¹ and H₃L⁹), or a third nitrogen atom, capable of participating in additional coordination (H₃L⁸, H₂L⁷ and H₃L¹¹). Reaction of Cu(NO₃)₂·6H₂O with the potassium salt of the N-thiophosphorylated thiourea NH₂C(S)NHP(S)(OiPr)₂ formed a new supramolecular Cu^I complex, [{Cu₆(H₂L¹)₆}{Cu₃(H₂L¹)₃}·4Me₂CO] that contains both trinuclear and hexanuclear forms in its solid state structure, and in solution.