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A Direct Carbon-13 and Nitrogen-15 NMR Study of Cerium(III)–Isothiocyanate Complexation in Aqueous Solvent Mixtures

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Abstract

A study of lanthanide complexation with isothiocyanate is underway using a multinuclear magnetic resonance technique. For isothiocyanate solutions in water–acetone–Freon mixtures at low temperature, −85–−125°C, ligand exchange is slow enough to permit the observation of 13C and 15N NMR signals for coordinated and free anions. For the Ce3+–NCS− system, four coordinated anion signals, displaced from the free anion signal by about +450 to +550 ppm for 15N and +50 to +80 ppm for 13C, are observed. The 13C and 15N spectral data are complementary, showing a signal area concentration dependence and measured coordination numbers consistent with the formation of Ce(NCS)2+ through Ce(NCS)1- 4. In water–methanol, the extent of complexing is decreased, presumably because of the higher dielectric constant of this medium. In addition, the results of a competitive study of NCS− and Cl− ion binding, carried out using 35Cl NMR, is presented.

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Authors and Affiliations

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

    Anthony Fratiello, Vicki Kubo-Anderson, Deborah J. Lee, Richard D. Perrigan & Kenneth Wong

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  1. Anthony Fratiello
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  2. Vicki Kubo-Anderson
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  3. Deborah J. Lee
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  4. Richard D. Perrigan
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Fratiello, A., Kubo-Anderson, V., Lee, D.J. et al. A Direct Carbon-13 and Nitrogen-15 NMR Study of Cerium(III)–Isothiocyanate Complexation in Aqueous Solvent Mixtures. Journal of Solution Chemistry 28, 193–210 (1999). https://doi.org/10.1023/A:1021754214188

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