Dependence of the stability of lanthanide β-dicarbonyl complexes on the metal—ligand bond energy

Mishchenko, AM, Trunova, EK
Dopov. Nac. akad. nauk Ukr. 2019, 4:74-80
https://doi.org/10.15407/dopovidi2019.04.074
Section: Chemistry
Language: Russian
Abstract: 

The formation constants of the lanthanide complexes with acetylacetone, methyl, and ethyl acetoacetate are determined by pH-potentiometric titration in a water-ethanol solution. Their stability is shown to correlate with the energy of the metal–ligand ionic bond calculated using the semiempirical Sparkle/PM7 method. Higher values of the overall formation constants of the lanthanide complexes with β-ketoesters are caused by the strengthening of the metal–ligand electrostatic interaction due to an increase of the negative charge on the ligand carbonyl oxygen atoms.

Keywords: formation constants, ionic bonding, lanthanide complexes, semiempirical calculations, β-dicarbonyl ligands
References: 

1. Skopenko, V. V., Amirkhanov, V. M., Sliva, T. Yu., Vasilchenko, I. S., Anpilova, E. L. & Garnovskii, A. D. (2004). Various types of metal complexes based on chelating β-diketones and their structural analogues. Russ. Chem. Rev., 73, pp. 737-752. doi: https://doi.org/10.1070/RC2004v073n08ABEH000909
2. Vigato, P. A., Peruzzo, V. & Tamburini, S. (2009). The evolution of β-diketone or β-diketophenol ligands and related complexes. Coord. Chem. Revs., 253, pp. 1099-1201. doi: https://doi.org/10.1016/j.ccr.2008.07.013
3. Wang, K.-Z. (2012). β-Diketonate. In The rare earth elements: fundamentals and applications (pp. 249-261). Chichester: Wiley.
4. Devi, R., Bala, M., Khatkar, S. P., Taxak, V. B. & Boora, P. (2016). Investigations of luminescent behavior and intramolecular energy transfer mechanism of europium(III) complexes with fluorinated β-ketoester ligand. J. Fluorine Chem., 181, pp. 36-44. doi: https://doi.org/10.1016/j.jfluchem.2015.11.004
5. Ivakha, N. B., Berezhnytska, O. S., Trunova, O. K., Savchenko, I. O., Smola, S. S. & Zheleznova, L. I. (2018). Allyl acetoacetate complexes of Nd(III), Er(III), Yb(III) as precursors of luminescent materials. Ukr. khim. zhurn., 84, No. 3, pp. 3-12 (in Ukrainian). doi: https://doi.org/10.1186/s11671-017-2074-0
6. Міshchenko, А. М. & Trunova, E. K. (2017). Study of complexation of lanthanide ions with methyl acetoacetate in water-ethanol solution. Ukr. khim. zhurn., 83, No. 9, pp. 11-21 (in Ukrainian).
7. Dutt, N. K. & Rahut, S. (1969). Chemistry of lanthanons-XXIII. The formation constants of the ethyl acetoacetato complexes of rare earths. J. Inorg. Nucl. Chem., 31, pp. 3177-3179. doi: https://doi.org/10.1016/0022-1902(69)80102-8
8. Mishchenko, A. M., Trunova, E. K. & Berezhnytska, A. S. (2015). Lanthanide complexes with allyl acetoacetate in mixed water-organic media: formation, stability and bonding. J. Solution Chem., 44, pp. 2117-2128. doi: https://doi.org/10.1007/s10953-015-0396-z
9. Albert, A. & Serjeant, E. P. (1962). Ionization constants of acids and bases: a laboratory manual. London: Methuen.
10. Dutra, J. D. L., Filho, M. A. M., Rocha, G. B., Freire, R. O., Simas, A. M. & Stewart, J. J. P. (2013). Sparkle/ PM7 lanthanide parameters for the modeling of complexes and materials. J. Chem. Theory Comput., 9, pp. 3333-3341. doi: https://doi.org/10.1021/ct301012h
11. Міshchenko, А. М. & Trunova, E. K. (2015). Semiempirical calculation of the structure of the aliphatic β-ketoesters tautomers. Ukr. khim. zhurn., 81, No. 10, pp. 73-80 (in Ukrainian).
12. Martynenko, L. I. (1991). Features of the complexation of trivalent rare earths. Russ. Chem. Rev., 60, pp. 1008-1022. doi: https://doi.org/10.1070/RC1991v060n09ABEH001125
13. Ionova, G., Rabbe, C., Guillaumont, R., Ionov, S., Madic, C., Krupa, J. C. & Guillaneux, D. (2002). A donor–acceptor model of Ln(III) complexation with terdentate nitrogen planar ligands. New J. Chem., 26, pp. 234-242. doi: https://doi.org/10.1039/b103996m
14. Karapetyans, M. Kh. & Drakin, S. I. (1978). Structure of matter. Moscow: Vishchaya shkola (in Russian).