A new calix[4] arene, functionalized with two thioamide moieties and with two allylic groups at the lower rim and the upper rim, respectively, and fixed in the 1,3-alternate conformation has been synthesized and its complexing properties towards Pb2+, Hg2+, Cd2+ and Na+ have been determined by UV-Vis titrations and by H-1 NMR spectroscopy in organic media. The stoichiometries of lead and mercury complexes (1 : 1) were at rst determined by the mole ratio method and by Job plots. The speciation of the two systems was obtained making use of two different multiwavelength and multivariate treatments of spectral data. The computer treatment of the data confirmed the 1 : 1 stoichiometry for the two complexes and gave reliable values for the corresponding stability constants (log K-Pb = 7.7; log K-Hg = 7.8). The ligand shows a high selectivity for lead and mercury over cadmium and sodium ions which are not complexed at all. Structural and conformational properties of the two complex species were obtained by H-1 NMR spectroscopy. H-1 NMR data show that, although having the same stoichiometry, the lead and mercury interact with the ligand molecule in a different manner.
Selective complexation of soft Pb2+ and Hg2+ by a novel allyl functionalized thioamide calix[4]arene in 1,3-alternate conformation: a UV-visible and H-1 NMR spectroscopic investigation
ARENA, Giuseppe;Contino A;SCIOTTO, Domenico;SPOTO, Giuseppe
2001-01-01
Abstract
A new calix[4] arene, functionalized with two thioamide moieties and with two allylic groups at the lower rim and the upper rim, respectively, and fixed in the 1,3-alternate conformation has been synthesized and its complexing properties towards Pb2+, Hg2+, Cd2+ and Na+ have been determined by UV-Vis titrations and by H-1 NMR spectroscopy in organic media. The stoichiometries of lead and mercury complexes (1 : 1) were at rst determined by the mole ratio method and by Job plots. The speciation of the two systems was obtained making use of two different multiwavelength and multivariate treatments of spectral data. The computer treatment of the data confirmed the 1 : 1 stoichiometry for the two complexes and gave reliable values for the corresponding stability constants (log K-Pb = 7.7; log K-Hg = 7.8). The ligand shows a high selectivity for lead and mercury over cadmium and sodium ions which are not complexed at all. Structural and conformational properties of the two complex species were obtained by H-1 NMR spectroscopy. H-1 NMR data show that, although having the same stoichiometry, the lead and mercury interact with the ligand molecule in a different manner.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
