Two new mixed aza-thia crowns 5-aza-2,8-dithia[9]-(2,9)-1,10-phenanthrolinophane (L-4) and 2,8-diaza-5-thia[9](2,9)-1,10-phenanthrolinophane (L-7) have been synthesized and characterized. The coordination behavior of L-4 and L-7 toward the metal ions Cu-II, Zn-II, Pb-II,Cd-II, Hg-II, and Ag-I was studied in aqueous solution by potentiometric methods, in CD3CN/D2O 4:1 (v/v) by H-1 NMR titrations and in the solid state. The data obtained were compared with those available for the coordination behavior toward the same metal ions of structurally analogous mixed donor macrocyclic ligands L-1-L-3, L-5, L-6: all these contain a phenanthroline subunit but have only S/O/N(aromatic) donor groups in the remaining portion of the ring and are, therefore, less water-soluble than L-4 and L-7. The complexes [Cd(NO3)(2)(L-5)], [Pb(L-7)](ClO4)(2) . 1/2MeCN, [Pb(L-4)](ClO4)(2) . MeCN, and [Cu(L-7)](ClO4)(2) . 3/2MeNO(2) were characterized by X-ray crystallography. The efficacy of L-1-L-7 in competitive liquid-liquid metal ion extraction of Cu-II, Zn-II, Cd-II, Pb-II, Ag-II, and Hg-II was assessed. In the absence of Hg-II, a clear extraction selectivity for Ag-I was observed in all systems investigated.
Interaction of mixed donor macrocycles containing the 1,10-phenanthroline subunit with selected transition metal ions: metal ion recognition in competitive liquid-liquid solvent extraction of Cu(II), Zn(II), Pb(II), Cd(II), Ag(I) and Hg(II) / M.C.Aragoni; M. Arca; A.Bencini; S. Biagini;A.J. Blake; C.Caltagirone; F.Demartin; G.De Filippo; F.A.Devillanova; A.Garau; K. Gloe; F. Isaia; V.Lippolis; B.Valtancoli; M.Wenzel. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - STAMPA. - 47:(2008), pp. 8391-8404. [10.1021/ic800548p]
Interaction of mixed donor macrocycles containing the 1,10-phenanthroline subunit with selected transition metal ions: metal ion recognition in competitive liquid-liquid solvent extraction of Cu(II), Zn(II), Pb(II), Cd(II), Ag(I) and Hg(II)
BENCINI, ANDREA;VALTANCOLI, BARBARA;
2008
Abstract
Two new mixed aza-thia crowns 5-aza-2,8-dithia[9]-(2,9)-1,10-phenanthrolinophane (L-4) and 2,8-diaza-5-thia[9](2,9)-1,10-phenanthrolinophane (L-7) have been synthesized and characterized. The coordination behavior of L-4 and L-7 toward the metal ions Cu-II, Zn-II, Pb-II,Cd-II, Hg-II, and Ag-I was studied in aqueous solution by potentiometric methods, in CD3CN/D2O 4:1 (v/v) by H-1 NMR titrations and in the solid state. The data obtained were compared with those available for the coordination behavior toward the same metal ions of structurally analogous mixed donor macrocyclic ligands L-1-L-3, L-5, L-6: all these contain a phenanthroline subunit but have only S/O/N(aromatic) donor groups in the remaining portion of the ring and are, therefore, less water-soluble than L-4 and L-7. The complexes [Cd(NO3)(2)(L-5)], [Pb(L-7)](ClO4)(2) . 1/2MeCN, [Pb(L-4)](ClO4)(2) . MeCN, and [Cu(L-7)](ClO4)(2) . 3/2MeNO(2) were characterized by X-ray crystallography. The efficacy of L-1-L-7 in competitive liquid-liquid metal ion extraction of Cu-II, Zn-II, Cd-II, Pb-II, Ag-II, and Hg-II was assessed. In the absence of Hg-II, a clear extraction selectivity for Ag-I was observed in all systems investigated.File | Dimensione | Formato | |
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