Abstract
Complexes of Np(V) with 1,10-phenanthroline-2,9-dicarboxylic acid, C12H6N2(COOH)2 (H2PDA), of the compositions [(NpO2)2(PDA)(H2O)3]·H2O (I), (NH4)2[NpO2(PDA)]2·3H2O (II), and [C(NH2)3]2[NpO2·(PDA)]2·4H2O (III) were synthesized. The Np atoms in the crystal lattices of all the compounds have the pentagonal bipyramidal coordination surrounding, with the [C12H6N2(COO)2]2− anions acting as chelate-bridging N,O-donor ligands. In the structure of I, two crystallographically independent NpO +2 dioxocations participate in the cation-cation interaction leading to the formation of tetrameric cation-cation complexes. The nonequivalence of the Np atoms is manifested in splitting of the main absorption band of Np(V) in the electronic spectrum of solid compound I. The structures of II and III are based on dimeric anionic complexes [NpO2(C12H6N2(COO)2)] 2−2 . Only one kind of complexes, NpO2(PDA)−, was detected in the solution, and high value of the concentration stability constant β, ∼1012 L mol−1, is due to tetradentate coordination of the ligand.
Similar content being viewed by others
References
Shi, Z.-F., Gao, Z.-Q., and Gu, J.-Z., Acta Crystallogr., Sect. E, 2010, vol. 66, no. 4, pp. m372–m373.
Moghimi, A., Alizadeh, R., Shokrollahi, A., et al., Inorg. Chem., 2003, vol. 42, no. 5, pp. 1616–1624.
Melton, D.L., VanDerveer, D.G., and Hancock, R.D., Inorg. Chem., 2006, vol. 45, no. 23, pp. 9306–9314.
Dean, N.E., Hancock, R.D., Cahill, C.L., and Frisch, M., Inorg. Chem., 2008, vol. 47, no. 6, pp. 2000–2010.
Ogden, M.D., Sinkov, S.I., Nilson, M., et al., J. Solution Chem., 2013, vol. 42, no. 1, pp. 211–225.
Dean, N.E., Metal Ion Complexing Properties of the Highly Preorganized Ligand 1,10-Phenanthroline-2,9-dicarboxylic Acid, MSc Thesis, Wilmington: Department of Chemistry, Univ. of North Carolina, 2007, http://libres.uncg.edu/ir/uncw/f/deann2007-1.pdf.
Gaver, C.R., Jr., The Highly Preorganized Ligands 8-(2-Pyridyl)Quinoline, 2,2′-Dipyridyl Amine and 1,10-Phenanthroline-2,9-dicarboxylic Acid and Their Complexing Properties with Metal Ions, MSc Thesis, Wilmington: Department of Chemistry, Univ. of North Carolina, 2008, http://libres.uncg.edu/ir/uncw/f/gaverc2008-1.pdf.
Sheldrick, G.M., SADABS, Madison, Wisconsin (USA): Bruker AXS, 2004.
Sheldrick, G.M., Acta Crystallogr., Sect. A, 2008, vol. 64, no. 1, pp. 112–122.
Nardelli, M., J. Appl. Crystallogr., 1999, vol. 21, no. 3, pp. 563–571.
Krot, N.N. and Grigor’ev, M.S., Usp. Khim., 2004, vol. 73, no. 1, pp. 94–106.
Burdet, F., Pécaut, J., and Mazzanti, M., J. Am. Chem. Soc., 2006, vol. 128, no. 51, pp. 16 512–16 513.
Nocton, G., Horeglad, P., Pécaut, J., and Mazzanti, M., J. Am. Chem. Soc., 2008, vol. 130, no. 49, pp. 16 633–16 645.
Copping, R., Mougel, V., Den Auwer, C., et al., Dalton Trans., 2012, vol. 41, no. 36, pp. 10 900–10 902.
Charushnikova, I.A., Krot, N.N., and Polyakova, I.N., Radiochemistry, 2005, vol. 47, no. 6, pp. 540–544.
Grigor’ev, M.S., Baturin, N.A., Regel’, L.L., and Krot, N.N., Radiokhimiya, 1991, vol. 33, no. 2, pp. 19–25.
Grigor’ev, M.S., Baturin, N.A., Budantseva, N.A., and Fedoseev, A.M., Radiokhimiya, 1993, vol. 35, no. 2, pp. 29–38.
Charushnikova, I.A., Perminov, V.P., and Katser, S.B., Radiokhimiya, 1995, vol. 37, no. 6, pp. 493–498.
Andreev, G.B., Antipin, M.Yu., Budantseva, N.A., and Krot, N.N., Koord. Khim., 2005, vol. 31, no. 11, pp. 844–847.
Bessonov, A.A., Budantseva, N.A., Fedoseev, A.M., et al., Radiokhimiya, 1990, vol. 32, no. 5, pp. 24–31.
Bessonov, A.A. and Krot, N.N., Radiochemistry, 2007, vol. 49, no. 6, pp. 571–574.
Bessonov, A.A., Afonas’eva, T.V., and Krot, N.N., Radiokhimiya, 1990, vol. 32, no. 5, pp. 31–35.
Bessonov, A.A. and Krot, N.N., Radiokhimiya, 1991, vol. 33, no. 3, pp. 35–46.
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © A.B. Yusov, I.A. Charushnikova, A.M. Fedoseev, A.A. Bessonov, 2014, published in Radiokhimiya, 2014, Vol. 56, No. 2, pp. 114–123.
Rights and permissions
About this article
Cite this article
Yusov, A.B., Charushnikova, I.A., Fedoseev, A.M. et al. Synthesis and structure of crystalline complexes of Np(V) with 1,10-phenanthroline-2,9-dicarboxylic acid. Complexation in solution and spectral studies. Radiochemistry 56, 134–144 (2014). https://doi.org/10.1134/S1066362214020027
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S1066362214020027