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A direct nitrogen-15 NMR study of cerium(III)-nitrate complexes in aqueous solvent mixtures

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Abstract

A study of the complex formation which occurs between cerium(III) and nitrate ions in aqueous solvent mixtures has been carried out by a direct, low-temperature, nitrogen-15 (15N) NMR technique. At temperatures in the range of −95 to −110°C, ligand exchange is slow enough to permit the observation of separate15N NMR signals for bulk nitrate, and this anion in the cerium(III) principal coordination shell. In water-acetone-Freon-12 mixtures, the spectra reveal the nitrato complexes do not form consecutively. Rather, signals are observed for Ce(NO3)2+, Ce(NO3) 1+2 , and only two other higher order complexes, even at very high NO −3 to Ce(III) mole ratios. Signal area evaluations were used to identify the possible higher order complexes. At comparable salt concentrations in aqueous-methanol mixtures, only Ce(NO3)2+ and Ce(NO3) 1+2 are formed, reflecting a decreased tendency for complexation in media of higher dielectric constant.

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Authors and Affiliations

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

    A. Fratiello, V. Kubo-Anderson, S. Azimi, E. Marinez, D. Matejka, R. Perrigan & B. Yao

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  1. A. Fratiello
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  2. V. Kubo-Anderson
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  3. S. Azimi
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Fratiello, A., Kubo-Anderson, V., Azimi, S. et al. A direct nitrogen-15 NMR study of cerium(III)-nitrate complexes in aqueous solvent mixtures. J Solution Chem 21, 651–666 (1992). https://doi.org/10.1007/BF00650759

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  • DOI: https://doi.org/10.1007/BF00650759

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