1. bookVolume 60 (2015): Issue 4 (December 2015)
Journal Details
License
Format
Journal
eISSN
1508-5791
First Published
25 Mar 2014
Publication timeframe
4 times per year
Languages
English
access type Open Access

Structure and separation quality of various N- and O-donor ligands from quantum-chemical calculations

Published Online: 30 Dec 2015
Volume & Issue: Volume 60 (2015) - Issue 4 (December 2015)
Page range: 847 - 851
Received: 18 Jun 2015
Accepted: 21 Aug 2015
Journal Details
License
Format
Journal
eISSN
1508-5791
First Published
25 Mar 2014
Publication timeframe
4 times per year
Languages
English
Abstract

Although BTP (2,6-di(1,2,4-triazin-3-yl)pyridine) has been proven to be a highly effective N-donor ligand for the selective An(III)/Ln(III) separation, the origin of its selectivity is still under discussion. We present in this paper quantum-chemical calculations at the density functional theory (DFT) and MP2 level which highlight the role of the aquo ions in the separation process. Furthermore these data will be the reference for future force-field development to investigate the differences in An(III) complexation reactions compared to their Ln(III) counterparts.

Keywords

1. Panak, P. J., & Geist, A. (2013). Complexation and extraction of trivalent actinides and lanthanides by triazinylpyridine N-donor ligands. Chem. Rev., 113, 1199-1236. DOI: 10.1021/cr3003399.10.1021/cr300339923360356Search in Google Scholar

2. Beele, B. B., Müllich, U., Schwörer, F., Geist, A., & Panak, P. J. (2012). Systematic modifications of BTP-type ligands and effects on the separation of trivalent lanthanides and actinides. Procedia Chem., 7, 146-151. DOI: 10.1016/j.proche.2012.10.025.10.1016/j.proche.2012.10.025Search in Google Scholar

3. Adam, C., Kaden, P., Beele, B. B., Müllich, U., Trumm, S., Geist, A., Panak, P. J., & Denecke, M. A. (2013). Evidence for covalence in a N-donor complex of americium(III). Dalton Trans., 42, 14068-14074. DOI: 10.1039/c3dt50953b.10.1039/c3dt50953b23752678Search in Google Scholar

4. Solomon, E. I., Hedman, B., Hodgson, K. O., Dey, A., & Szilagyi, R. K. (2005). Ligand K-edge X-ray absorption spectroscopy: covalency of ligand-metal bonds. Coord. Chem. Rev., 249, 97-129. DOI: 10.1016/j. ccr.2004.03.020.Search in Google Scholar

5. Neidig, M. L., Clark, D. L., & Martin, R. L. (2013). Covalency in f-element complexes. Coord. Chem. Rev., 257, 394-406. DOI: 10.1016/j.ccr.2012.04.029.10.1016/j.ccr.2012.04.029Search in Google Scholar

6. Kaltsoyannis, N. (2013). Does covalency increase or decrease across the actinide series? Implications for minor actinide partitioning. Inorg. Chem., 52, 3407-3413. DOI: 10.1021/ic3006025.10.1021/ic300602522668004Search in Google Scholar

7. Bryantsev, V. S., & Hay, B. P. (2015). Theoretical prediction of Am(III)/Eu(III) selectivity to aid the design of actinide-lanthanide separation agents. Dalton Trans., 44, 7935-7942. DOI: 10.1039/c4dt03275f.10.1039/C4DT03275F25824656Search in Google Scholar

8. De Sahb, C., Watson, L. A., Nadas, J., & Hay, B. P. (2013). Design criteria for polyazine extractants to separate An(III) from Ln(III). Inorg. Chem., 52, 10632-10642. DOI: 10.1021/ic401666m.10.1021/ic401666m23971900Search in Google Scholar

9. Huang, Q. -R., Kingham, J. R., & Kaltsoyannis, N. (2015). The strength of actinide-element bonds from the quantum theory of atoms-in-molecules. Dalton Trans., 44, 2554-2566. DOI: 10.1039/c4dt02323d.10.1039/C4DT02323DSearch in Google Scholar

10. Petit, L., Adamo, C., & Maldivi, P. (2006). Toward a clear-cut vision on the origin of 2,6-di(1,2,4-triazin-3-yl)pyridine selectivity for trivalent actinides: Insights from theory. Inorg. Chem., 45, 8517-8522. DOI: 10.1021/ic060227g.10.1021/ic060227g17029362Search in Google Scholar

11. Guillaumont, D. (2004). Quantum chemistry study of actinide(III) and lanthanide(III) complexes with tridentate nitrogen ligands. J. Phys. Chem., 108, 6893-6900. DOI: 10.1021/jp048550x.10.1021/jp048550xSearch in Google Scholar

12. Maldivi, P., Petit, L., Adamo, C., & Vetere, V. (2007). Theoretical description of metal ligand bonding within f-element complexes: A successful and necessary interplay between theory and experiment. C. R. Chimie, 10, 888-896. DOI: 10.1016/j.crci.2006.12.011.10.1016/j.crci.2006.12.011Search in Google Scholar

13. Narbutt, J., Wodyński, A., & Pecul, M. (2015). The selectivity of diglycolamide (TODGA) and bis-triazine- -bipyridine (BTBP) ligands in actinide/lanthanide complexation and solvent extraction separation - a theoretical approach. Dalton Trans., 44, 2657-2666. DOI: 10.1039/c4dt02657h.10.1039/C4DT02657HSearch in Google Scholar

14. Becke, A. D. (1993). A new mixing of Hartree-Fock and local density-functional theories. J. Chem. Phys., 98, 1372-1377. DOI: 10.1063/1.464304.10.1063/1.464304Search in Google Scholar

15. TURBOMOLE V6.4. (2012). A development of University of Karlsruhe and Forschungszentrum Karlsruhe GmbH, 1989-2007, TURBOMOLE GmbH, since 2007. Available from http://www.turbomole.com.Search in Google Scholar

16. Küchle, W., Dolg, M., Stoll, H., & Preuss, H. (1994). Energy-adjusted pseudopotentials for the actinides - parameter sets and test calculations for thorium and thorium monoxide. J. Chem. Phys., 100, 7535-7542. DOI: 10.1063/1.466847.10.1063/1.466847Search in Google Scholar

17. Weigend, F., & Häser, M. (1997). RI-MP2: First derivatives and global consistency. Theor. Chem. Acc., 97, 331-340. DOI: 10.1007/s002140050269.10.1007/s002140050269Search in Google Scholar

18. Weigend, F., Häser, M., Patzelt, H., & Ahlrichs, R. (1998). RI-MP2: Optimized auxiliary basis sets and demonstrations of effi ciency. Chem. Phys. Lett., 294, 143-152. DOI: 10.1016/S0009-2614(98)00862-8.10.1016/S0009-2614(98)00862-8Search in Google Scholar

19. Boys, S. F., & Bernardi, F. (1970). The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors. Mol. Phys., 19, 553-566. DOI: 10.1080/00268977000101561.10.1080/00268977000101561Search in Google Scholar

20. Klamt, A., & Schüürmann, G. (1993). COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient. J. Chem. Soc. Perkin Trans., 2, 799-805. DOI: 10.1039/p29930000799.10.1039/P29930000799Search in Google Scholar

21. Ho, J., Klamt, A., & Coote, M. L. (2010). Comment on the correct use of continuum solvent models. J. Phys. Chem., 114, 13442-13444. DOI: 10.1021/jp107136j.10.1021/jp107136j21133342Search in Google Scholar

22. Réal, F., Trumm, M., Vallet, V., Schimmelpfennig, B., Masella, M., & Flament, J. -P. (2010). Quantum-chemical and molecular dynamics study of the coordination of Th(IV) in aqueous solvent. J. Chem. Phys. B, 114, 15913-15924. DOI: 10.1021/jp108061s.10.1021/jp108061s21070066Search in Google Scholar

23. Réal, F., Trumm, M., Schimmelpfennig, B., Masella, M., & Vallet, V. (2013). Further insights in the ability of classical nonadditive potentials to model actinide ion-water interactions. J. Comp. Chem., 34, 707-719. DOI: 10.1002/jcc.23184.10.1002/jcc.23184Search in Google Scholar

24. Borrini, J., Favre-Reguillon, A., Lemaire, M., Gracia, S., Arrachart, G., Bernier, G., Hérès, X., & Hill, C. (2015). Water soluble PDCA derivatives for selective Ln(III)/An(III) and Am(III)/Cm(III) separation. Solvent Extr. Ion Exch., 33, 224-235. DOI: 10.1080/07366299.2014.974449.10.1080/07366299.2014.974449Search in Google Scholar

25. Trumm, S., Geist, A., Panak, P. J., & Fanghänel, T. (2011). An improved hydrolytically-stable bis- -triazinyl-pyridine (BTP) for selective actinide extraction. Solvent Extr. Ion Exch., 29, 213-229. DOI: 10.1080/07366299.2011.539129.10.1080/07366299.2011.539129Search in Google Scholar

26. Hudson, M. J., Boucher, C. E., Braekers, D., Desreux, J. F., Drew, M. G. B., Foreman, M. R. S., Harwood, L. M., Hill, C., Madic, C., Marken, F., & Youngs, T. G. A. (2006). New bis(triazinyl)pyridines for selective extraction of americium(III). New J. Chem., 30, 1171-1183. DOI: 10.1039/b514108g.10.1039/b514108gSearch in Google Scholar

27. Boucher, C., Drew, M. G. B., Giddings, P., Harwood, L. M., Hudson, M. J., Iveson, P. B., & Madic, C. (2002). 12-coordinate complexes formed by the early lanthanide metals with 2,6-bis(-1,2,4-triazin-3-yl)- pyridin. Inorg. Chem. Commun., 5, 596-599. DOI: 10.1016/S1387-7003(02)00489-6.10.1016/S1387-7003(02)00489-6Search in Google Scholar

28. Kolarik, Z., Müllich, U., & Gassner, F. (1999). Selective extraction of Am(III) over Eu(III) by 2,6-ditriazolyland 2,6-ditriazinylpyridines. Solvent Extr. Ion Exch., 17, 1155-1170. DOI: 10.1080/07366299908934641.10.1080/07366299908934641Search in Google Scholar

29. Morgan, G. T., & Burstall, F. H. (1932). Dehydrogenation of pyridine by anhydrous ferric chloride. J. Chem. Soc., 20-30.10.1039/jr9320000020Search in Google Scholar

30. Drew, M. G. B., Foreman, M. R. S. J., Hill, C., Hudson, M. J., & Madic, C. (2005). 6,6ʹ-bis-(5,6-diethyl-[1,2,4] triazin-3-yl)-2,2ʹ-bipyridyl the first example of a new class of quadridentate hetercyclic extraction reagents for the separation of americium(III) and europium(III). Inorg. Chem. Commun., 8, 239-241. DOI: 10.1016/j.inoche.2004.12.017.10.1016/j.inoche.2004.12.017Search in Google Scholar

31. Bremer, A., Ruff, C. M., Girnt, D., Müllich, U., Rothe, J., Roesky, P. W., Panak, P. J., Karpov, A., Müller, T. J. J., Denecke, M. A., & Geist, A. (2012). 2,6-bis(5- (2,2-dimethylpropyl)-1H-pyrazol-3-yl)pyridine as a ligand for efficient actinide(III)/lanthanide(III) separation. Inorg. Chem., 51, 5199-5207. DOI: 10.1021/ic3000526.10.1021/ic300052622515352Search in Google Scholar

32. Sasaki, Y., Tsubata, Y., Kitatsuji, Y., Sugo, Y., Shirasu, N., Morita, Y., & Kimura, T. (2013). Extraction behavior of metal ions by TODGA, DOODA, MIDOA, and NTAamide extractants from HNO3 to n-Dodecane. Solvent Extr. Ion Exch., 31, 401-415. DOI: 10.1080/07366299.2013.800431.10.1080/07366299.2013.800431Search in Google Scholar

33. Beele, B., Skerencak-Frech, A., Trumm, M., & Schimmelpfennig, B. (2015). BTP a highly selective N-donor ligand studied by TRLFS and liquid-liquid extraction. (in preparation).Search in Google Scholar

34. Hagström, I., Spjuth, L., Enarsson, A., Liljenzin, J. O., Skalberg, M., Hudson, M. J., Iveson, P. B., Madic, C., Cordier, P. Y., Hill, C., & Francois, N. (1999). Synergistic solvent extraktion of trivalent americium and europium by 2-bromodecanoic acid and neutral nitrogen-containing reagents. Solvent Extr. Ion Exch., 17, 221-242. DOI: 10.1080/07366299908934610.10.1080/07366299908934610Search in Google Scholar

35. Clavaguéra, C., & Dognon, J. P. (2005). Accurate static electric dipole polarizability calculations of +3 charged lanthanide ions. Chem. Phys., 311, 169-176. DOI: 10.1016/j.chemphys.2004.10.014.10.1016/j.chemphys.2004.10.014Search in Google Scholar

Recommended articles from Trend MD

Plan your remote conference with Sciendo