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)(2)

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 AgI 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 C=S groups (H3L1 and H3L9), or a third nitrogen atom, capable of participating in additional coordination (H3L8, H2L7 and H3L11). Reaction of Cu(NO3)(2)center dot 6H(2)O with the potassium salt of the N-thiophosphorylated thiourea NH2C(S)NHP(S)(OiPr)(2) formed a new supramolecular Cu-I complex, [{Cu-6(H2L1)(6)}{Cu-3(H2L1)(3)}center dot 4Me(2)CO] that contains both trinuclear and hexanuclear forms in its solid state structure, and in solution.