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.
Similar content being viewed by others
References
Lanthanide Probes in Life, Chemical and Earth Sciences, J.-C. G. Bünzli and G. R. Choppin (eds.) (Elsevier, Amsterdam, 1989).
Biochemistry of the Lanthanides, C. H. Evans, (Plenum Press, New York, 1990).
Lanthanides in Organic Synthesis, T. Imamoto, (Academic Press, New York, 1994).
A. Tsubouchi and T. Bruice,J. Am. Chem. Soc. 116, 11614 (1994).
J. Huskens, A. D. Kennedy, H. Van Bekhum, and J. A. Peters,J. Am. Chem. Soc. 117, 375 (1995).
H. B. Silber, T. Parker, and N. Nguyen,J. Alloys Compd. 180, 369 (1992).
D. T. Cronce and W. De W. Horrocks, Jr., Biochemistry,31, 7963 (1992).
H. A. Tajmir-Riahi, R. Ahmad, and M. Naoui,J. Biomol. Struct. Dyn. 10, 863 (1993).
D. J. Calvo, A. E. Vazquez, and R. Miledi,Proc. Natl. Acad. Sci. U.S.A. 91, 12725 (1994).
K. K. Karukstis, M. Y. Kao, D. A. Savin, R. A. Bittker, K. J. Kaphengst, C. M. Emetarom, N. R. Naito, and D. Y. Takamoto,J. Phys. Chem. 99, 4339 (1995).
I. E. Hill, C. W. V. Hogue, I. D. Clark, J. P. MacManus, and A. G. Szabo,Anal. Biochem. 216, 439 (1994).
S. E. Burroughs, W. DeW. Horrocks, Jr., H. Ren, and C. B. Klee,Biochemistry 33, 10428 (1994).
J.-C. G. Bünzli and J. M. Pfefferie,Helv. Chim. Acta 77, 323 (1994).
D. H. White, L. A. De Learie, D. A. Moore, R. A. Wallace, T. J. Dunn, W. P. Cacheris, H. Imura, and G. Choppin,Invest. Radiol. 26, (Suppl. 1) S226 (1991).
J. L. Sessler, T. D. Mody, G. W. Hemmi, V. Lynch, S. W. Young, and R. A. Miller,J. Am. Chem. Soc. 115, 10368 (1993).
K. Micskei, D. H. Powell, L. Helm, E. Brucher, and A. E. Merbach,Magn. Reson. Chem. 31, 1011 (1993).
K. Micskei, L. Helm, E. Brucher, and A. E. Merbach,Inorg. Chem. 32, 3844 (1993).
G. Gonzalez, D. H. Powell, V. Tissieres, and A. E. Merbach,J. Phys. Chem. 98, 53 (1994).
H. D. Powell, G. Gonzalez, V. Tissieres, K. Micskei, E. Brucher, L. Helm, and A. E. Merbach,J. Alloys Compd. 207, 20 (1994).
J. Lisowski, J. L. Sesler, V. Lynch, and T. D. Mody,J. Am. Chem. Soc. 117, 2273 (1995).
R. Ramasamy, D. Mota De Freitas, C. F. G. C. Geraldes, and J. A. Peters,Inorg. Chem. 30, 3188 (1991).
L. Helm and A. E. Merbach,Eur. J. Solid State Inorg. Chem. 28 (Suppl.), 245 (1991).
J.-C. G. Bünzli and V. Kaspararek,Inorg. Chim. Acta 182, 101 (1991).
S. Aime, M. Botta, and G. Ermondi,Inorg. Chem. 31, 4291 (1992).
C. F. G. C. Geraldes, A. D. Sherry, and G. E. Kiefer,J. Magn. Reson. 97, 290 (1992).
A. Milicic-Tang and J.-C. G. Bünzli,Inorg. Chim. Acta 192, 201 (1992).
J.-C. G. Bünzli, A. Milicic-Tang, and C. Mabillard,Helv. Chim. Acta 76, 1292 (1993).
J.-C. G. Bünzli, P. Froidevaux, and J. M. Harrowfield,Inorg. Chem. 32, 3306 (1993).
C. F. G. C. Geraldes, A. M. Urbano, M. A. Hoefnagel, and J. A. Peters,Inorg. Chem. 32, 2426 (1993).
S. J. Franklin and K. N. Raymond,Inorg. Chem. 33, 5794 (1994).
K. Nakumura, T. Yamaguchi, H. Wakita, M. Nomura, and G. R. Choppin,Kidorui 24, 100 (1994).
L. Helm, F. Foglia, T. Kowall, and A. E. Merbach,J. Phys. Condens. Matter 6, (Suppl. 23A), A 137 (1994).
R. K. Agarual, H. Agarual, and R. K. Sarlin,Synth. React. Inorg. Met.-Org. Chem. 24, 1681 (1994).
Th. Kowall, F. Foglia, L. Helm, and A. E. Merbach,J. Am. Chem. Soc. 117, 3790 (1995).
C. Cossy, L. Helm, D. H. Powell, and A. E. Merbach,New J. Chem. 19, 27 (1995).
H. B. Silber, R. Bakhshandehfar, L. A. Contreras, F. Gaizer, M. Gonsalves, and S. Ismail,Inorg. Chem. 29, 4473 (1990).
S. Lis and G. R. Choppin,Anal. Chem. 63, 2542 (1991).
J.-C. G. Bünzli,J. Alloys Compd. 192, 266 (1993).
H. B. Silber and R. L. Campbell,J. Alloys Compd. 192, 262 (1993).
H. Jing, X. Wang, Z. Hou, S. Chen, and D. Li,Polyhedron 13, 1035 (1994).
J.-C. G. Bünzli and J. P. Metabanzoulou,Helv. Chim. Acta 77, 140 (1994).
A. Fratiello, V. Kubo-Anderson, T. Bolinger, C. Cordero, B. DeMerit, T. Flores, and R. Perrigan,J. Solution Chem. 18, 313 (1989).
A. Fratiello, V. Kubo-Anderson, T. Bolinger, C. Cordero, B. DeMerit, T. Flores, D. Matejka, and R. Perrigan,J. Magn. Reson. 83, 358 (1989).
A. Fratiello, V. Kubo-Anderson, E. L. Bolanos, D. Haigh, F. Laghaei, and R. D. Perrigan,J. Magn. Reson. Series A107, 56 (1994).
A. Fratiello, V. Kubo-Anderson, S. Azimi, T. Flores, E. Marinez, D. Matejka, R. Perrigan, and M. Vigil,J. Solution Chem. 19, 811 (1990).
A. Fratiello, V. Kubo-Anderson, S. Azimi, E. Marinez, D. Matejka, R. Perrigan, and B. Yao,J. Solution Chem. 20, 893 (1991).
A. Fratiello, V. Kubo-Anderson, S. Azimi, E. Marinez, D. Matejka, R. Perrigan, and B. Yao,J. Solution Chem. 21, 651 (1992).
A. Fratiello, V. Kubo-Anderson, S. Azimi, F. Laghaei, R. D. Perrigan, and F. Reyes,J. Solution Chem. 21, 1015 (1992).
A. Fratiello, V. Kubo-Anderson, S. Azimi, O. Chavez, F. Laghaei, and R. D. Perrigan,J. Solution Chemistry 22, 519 (1993).
A. Fratiello, V. Kubo-Anderson, E. L. Bolanos, O. Chavez, F. Laghaei, J. V. Ortega, and R. D. Perrigan,J. Solution Chem. 23, 1019, (1994).
A. Fratiello, V. Kubo-Anderson, S. Azimi, C. Fowler, E. Marinez, R. Perrigan, S. Shayegan, B. Yao,Magn. Reson. Chem. 30, 280 (1992).
A. Fratiello, V. Kubo-Anderson, E. Bolanos, O. Chavez, J. V. Ortega, R. D. Perrigan, A. Reyes, and S. M. Stoll,Magn. Reson. Chem. 33, 431 (1995).
A. Fratiello, V. Kubo-Anderson, A. Adanalyan, E. L. Bolanos, J. V. Ortega, R. D. Perrigan, and L. Saenz,J. Solution Chem. 24, 1249 (1995).
G. E. Pake,Paramagnetic Resonance (W. A. Benjamin, New York, 1962).
W. DeW. Horrocks, Jr., J. P. Sipe, III, and D. Sudnick,Nuclear Magnetic Resonance Shift Reagents, Ed. by R. E. Sievers, Acad. Press, Inc., p. 53 (1973).
S. W. Hall, L. R. Avens, D. K. Veirs, and B. D. Zwick,203rd ACS Natl. Mtg. Abstracts, San Francisco, CA (1992).
H. Wang, S. Zhao, P. Qian, Z. Cao, and K. Yu,Polyhedron 14, 407 (1995).
J.-C. Bünzli and M. M. Vuckovic,Inorg. Chim. Acta 73, 53 (1983).
J. C. Bünzli and J.-R. Yersin,Inorg. Chim. Acta 94, 301 (1984).
J.-C. G. Bünzli and C. Mabillard,New Front. Rare Earth Sci. Appl., Proc. Int. Conf. Rare Earth Dev. Appl. 1, 250 (1985).
D. H. Metcalf, R. C. Carter, R. G. Ghiradelli, and R. A. Palmer,Inorg. Chem. 25, 2175 (1986).
D. L. Nelson and D. E. Irish,J. Chem. Soc. Far. Trans. I,69, 156 (1973).
H. B. Silber and Max S. Trozier,Inorg. Chim. Acta 128, 267 (1987).
H. B. Silber,Inorg. Chim. Acta 33, 139 (1987).
M. L. Steele and D. L. Wertz,J. Am. Chem. Soc. 98, 4424 (1976).
L. S. Smith, Jr. and D. L. Wertz,J. Am. Chem. Soc. 97, 2365 (1975).
L. S. Smith, Jr., D. C. McCain, and D. L. Wertz,J. Am. Chem. Soc. 98, 5125 (1976).
H. B. Silber, D. Bouler, and T. White,J. Phys. Chem. 82, 775 (1978).
H. B. Silber and T. Mioduski,Inorg. Chem. 23, 1577 (1984).
H. A. Berman and T. R. Stengle,J. Phys. Chem. 79, 1001 (1975).
H. A. Berman, H. J. C. Yeh, and T. R. Stengle,J. Phys. Chem. 79, 2551 (1975).
J. B. Lambert and W. Schilf,J. Am. Chem. Soc. 110, 6364 (1988).
A. Fratiello, R. E. Lee, V. M. Nishida, and R. E. Schuster,Inorg. Chem. 8, 69 (1969).
F. Tanaka, Y. Kawasaki, and S. Yamashita,J. Chem. Soc. Far. Trans I,84, 1083 (1988).
A. Fratiello, V. Kubo-Anderson, A. Adanalyan, E. Bolanos, J. Ortega, R. D. Perrigan, V. San Lucas, and A. Wong, unpublished results.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
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
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF00972891