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

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 (13). The best extraction properties have been shown by (3)L(1), (3)L(8), (2)L(7), (3)L(9) and (3)L(11) which contain an unsubstituted nitrogen atom at the C[double bond, length as m-dash]S groups ((3)L(1) and (3)L(9)), or a third nitrogen atom, capable of participating in additional coordination ((3)L(8), (2)L(7) and (3)L(11)). Reaction of Cu(NO(3))(2).6H(2)O with the potassium salt of the N-thiophosphorylated thiourea NH(2)C(S)NHP(S)(OiPr)(2) formed a new supramolecular Cu(I) complex, [{Cu(6)((2)L(1))(6)}{Cu(3)((2)L(1))(3)}.4Me(2)CO] that contains both trinuclear and hexanuclear forms in its solid state structure, and in solution.

Synthesis of a new α-aminophosphonate library. Crystal structure of p-XC6H4–NH–CH(p-BrC6H4)–P(O)(OiPr)2 (X = H, Br, CH3O)

“…The interest is caused not only from the fact that these compounds show a rich coordination chemistry but also from the applications of (thio)phosphoryl(thio)ureas as agents for extraction and transporting different cations, anions and organic molecules [14], and as ligands in metal complexes used as single source precursors for thin films, nanocrystals and semiconductors [15]. One of the pathways to new (thio)phosphoryl (thio)urea ligands is the modification of amines (Scheme 1).…”

The Trinuclear Copper(I) Thiolate Complexes[Cu3(NGuaS)3]0/1+ and their Dimeric Variants [Cu6(NGuaS)6]1+/2+/3+ with Biomimetic Redox Properties

“…The basic structural difference between this compound and 2 lies-besides the different metal oxidation state-in the chemical identity and the arrangement of the exogenous bound ligand donor functions which in the Cu I compound belong to the same Cu 3 S 3 ring as the bridging thiolate sulfur functions contrasting the situation in 2. [14] The individual {Cu 2 S 2 } unit of 2 is a structural model for the core portion of the Cu A center of cytochrome-c oxidases (and N 2 O reductases), and the oxidation state of the copper atoms in the oxidized form 2 ox coincides with the oxidized form of the biological system. [15] This similarity also applies to the Cu···Cu distance of 2.598 which is only slightly shorter in the biological system.…”