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A direct carbon-13 and nitrogen-15 NMR study of europium(III) complexation-nitrate and europium(III)-isothiocyanate complexation in aqueous solvent mixtures

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Abstract

A direct, low-temperature nuclear magnetic resonance spectroscopic study of europium(III)-nitrate contact ion-pairing has been completed, and preliminary results for europium(III)-isothiocyanate have been obtained. In water-acetone-Freon mixtures, at −110°C to −120°C, four15N NMR signals are observed for coordinated nitrate ion. Area evaluations of the signals and their concentration dependence indicate the formation of Eu(NO3)2+, Eu(NO3) 1+2 , and two higher complexes, possibly the tetra-, with either the penta-or hexanitrato. This correlates well with similar15N NMR results obtained for Ce(III), Pr(III), Nd(III), and Sm(III). As a result of a higher dielectric constant, complex formation is significantly less in water-methanol mixtures, wheein only three complexes form with Eu(NO3) 1+2 dominating at the highest anion concentrations. Competitive complexing experiments in water-methanol also were made by35Cl NMR chemical shift and linewidth measurements, as well as15N NMR. Initial experiments with the Eu3+-NCS− system show four coordinated anion signals, displaced from the bulk anion peak by about −250 ppm and −2,500 ppm in the13C and15N NMR spectra, respectively. Area evaluations are consistent with the presence of Eu(NCS)2+ through Eu(NCS) 1-4 in these solutions. A consideration of the chemical shifts identified the nitrogen atom as the site of binding in the NCS−. A discussion of these preliminary results, as well as those for several other metal-ions, will be presented.

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  1. Department of Chemistry and Biochemistry, California State University, Los Angeles, 90032, Los Angeles, California

    A. Fratiello, V. Kubo-Anderson, E. Bolanos, O. Chavez, J. Ortega, R. D. Perrigan, F. Reyes, L. Saenz, S. M. Stoll & T. Thompson

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Fratiello, A., Kubo-Anderson, V., Bolanos, E. et al. A direct carbon-13 and nitrogen-15 NMR study of europium(III) complexation-nitrate and europium(III)-isothiocyanate complexation in aqueous solvent mixtures. J Solution Chem 25, 345–367 (1996). https://doi.org/10.1007/BF00972891

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