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Lanthanide Complexes with Allyl Acetoacetate in Mixed Water–Organic Media: Formation, Stability and Bonding

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Abstract

The equilibrium between unsaturated \(\beta \)-ketoester allyl acetoacetate and certain lanthanide ions (La3+, Pr3+, Nd3+, Sm3+, Gd3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+) was studied in mixed dioxane–water–ethyl acetate media. The formation of cationic 1:1 and 1:2 type complexes was shown and their formation constants were determined by potentiometric titration. For the 1:2 type complexes a molecular mechanics geometry optimization was performed and the bonding parameters were calculated on the basis of their electronic absorption spectra using the lanthanide aqua-ions as reference standards. The correlation between the nephelauxetic ratio and the relative metal–ligand bond length shortening due to the complexation was revealed and clarified.

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References

  1. Katkova, M.A., Vitukhnovsky, A.G., Bochkarev, M.N.: Coordination compounds of rare-earth metals with organic ligands for electroluminescent diodes. Russ. Chem. Rev. 74, 1089–1109 (2005)

    Article  CAS  Google Scholar 

  2. Eliseeva, S., Bünzli, J.-C.G.: Lanthanide luminescence for functional materials and bio-sciences. Chem. Soc. Rev. 39, 189–227 (2010)

    Article  CAS  Google Scholar 

  3. Yatsimirskii, K.B., Kostromina, N.A., Sheka, Z.A., Davidenko, N.K., Kriss, E.E., Ermolenko, V.I.: Khimiya kompleksnykh soedinenii redkozemel’nykh elementov (Chemistry of the complex compounds of the rare-earth elements). Naukova Dumka, Kiev (1966)

    Google Scholar 

  4. Binnemans, K.: Rare-earth beta-diketonates. In: Gschneidner Jr, K.A., Bünzli, J.-C.G., Pecharsky, V.K. (eds.) Handbook on the Physics and Chemistry of Rare Earths, vol. 35, pp. 107–272. Elsevier, North-Holland (2005)

    Google Scholar 

  5. Huang, C. (ed.): Rare Earth Coordination Chemistry: Fundamentals and Applications. Wiley (Asia), Singapore (2010)

  6. Sankha, B.S., Kapoor, R.N.: Organic compounds of samarium. II. Reactions of samarium isopropoxide with ethyl acetoacetate. Can. J. Chem. 44, 1369–1372 (1966)

    Article  Google Scholar 

  7. Poluektov, N.S., Drobyazko, V.N., Beltyukova, S.V., Kononenko, L.I.: Spectrophotometric study of neodymium(III), holmium(III) and erbium(III) ions complexation with acetoacetic ester. Koord. Khimiya 3, 476–479 (1977)

    CAS  Google Scholar 

  8. Dutt, N.K., Rahut, S.: Chemistry of lanthanons—XXIII. The formation constsnts of the ethyl acetoacetato complexes of rare earth. J. Inorg. Nucl. Chem. 31, 3177–3179 (1969)

    Article  CAS  Google Scholar 

  9. Dutt, N.K., Rahut, S.: Chemistry of lanthanons—XXVII. Rare earth complexes of ethylacetoacetate. J. Inorg. Nucl. Chem. 32, 2905–2909 (1970)

    Article  CAS  Google Scholar 

  10. Hubert-Pfalzgraf, L.G., Miele-Pajot, N., Papiernik, R., Vaissermann, J.: A novel example of self-assembly in lanthanide chemistry: Synthesis and molecular structure of [Na(EtOH)6][Y9(μ4-O)2(μ3-OH)8{μ-η2-MeC(O)CHC(O)OEt}8{η2-MeC(O)CHC(O)OEt}8]. J. Chem. Soc., Dalton Trans. 23, 4127–4130 (1999)

    Article  Google Scholar 

  11. Souza, A.P., Alves Jr, S., Malta, O.L.: New complexes of europium and gadolinium with 2,4,6-trichlorophenyl acetoacetate as ligand. Opt. Mater. 33, 402–407 (2011)

    Article  CAS  Google Scholar 

  12. Cauro-Gamet, L.C., Hubert-Pfalzgraf, L.G., Lecocq, S.: Syntheses and molecular structures of titanium derivatives with polymerizable ligands. Toward extended arrays. Z. Anorg. Allg. Chem. 630, 2071–2077 (2004)

    Article  CAS  Google Scholar 

  13. Godlewska-Żylkiewicz, B., Zambrzycka, E., Leśniewska, B., Wilczewska, A.Z.: Separation of ruthenium from environmental samples on polymeric sorbent based on imprinted Ru(III)–allyl acetoacetate complex. Talanta 89, 352–359 (2012)

    Article  Google Scholar 

  14. Mishchenko, A.M., Trunova, E.K., Berezhnytskaya, A.S., Rogovtsov, A.A.: Tendency of the nephelauxetic effect to vary in a series of lanthanide complexes with allyl acetoacetate. J. Appl. Spectrosc. 81, 905–911 (2015)

    Article  CAS  Google Scholar 

  15. Martynenko, L.I.: Features of the complexation of trivalent rare earths. Russ. Chem. Rev. 60, 1008–1022 (1991)

    Article  Google Scholar 

  16. Tsuchiya, T., Taketsugu, T., Nakano, H., Hirao, K.: Theoretical study of electronic and geometric structures of a series of lanthanide trihalides LnX\(_{\text{3 }}\) (Ln = La–Lu; X = Cl, F). J. Mol. Struct. (Theochem) 461–462, 203–222 (1999)

    Article  Google Scholar 

  17. Choppin, G.R.: Covalency in f-element bonds. J. Alloys Compd. 344, 55–59 (2002)

    Article  CAS  Google Scholar 

  18. Tanner, P.A., Yeung, Y.Y.: Nephelauxetic effects in the electronic spectra of Pr3+. J. Phys. Chem. A 117, 10726–10735 (2013)

    Article  CAS  Google Scholar 

  19. Tsaryuk, V., Zolin, V., Legendziewicz, J.: The structure of ligands and effects of the europium luminescence excitation. J. Lumin. 102–103, 744–750 (2003)

    Article  Google Scholar 

  20. Dutt, N.K., Nag, K., Seshadri, T.: Chemistry of lanthanons—XX. Complexes of the rare earths with 3-mercapto-1-phenylbut-2-en-1-one. J. Inorg. Nucl. Chem. 31, 1435–1438 (1969)

    Article  CAS  Google Scholar 

  21. Pashchevskaya, N.V., Bolotin, S.N., Sokolov, M.E., Sklyar, A.A., Panyushkin, V.T.: Potentiometric study of reactions of rare-earth elements with 3-allylpentanedione in a water–dioxane medium. Russ. J. Gen. Chem. 76, 1011–1014 (2006)

    Article  CAS  Google Scholar 

  22. Davidenko, N.K., Zholdakov, A.A.: Stability of the benzoyl acetonate complexes of the rare earth elements in water–methanol solution. Z. Neorg. Khimii 12, 1195–1198 (1967)

    CAS  Google Scholar 

  23. Mumper, R.J., Jay, M.: Formation and stability of lanthanide complexes and their encapsulation into polymeric microspheres. J. Phys. Chem. 96, 8626–8636 (1992)

    Article  CAS  Google Scholar 

  24. Hartley, F., Burgess, C., Alcock, R.: Solution Equilibria. Ellis Horwood, Chichester (1980)

    Google Scholar 

  25. Irving, H., Rossotti, H.: The calculation of formation curves of metal complexes from pH titration curves in mixed solvents. J. Chem. Soc. 2904–2910 (1954)

  26. Bayes, G.S., Raut, S.S., Patil, V.R., Lokhande, R.S.: Formation of diazepam–lanthanides(III) complexes in the 50–50 volume % ethanol–water solvent system and study of the effect of temperature on the complex formation constants. J. Solution Chem. 41, 241–248 (2012)

    Article  CAS  Google Scholar 

  27. HyperChem version 8.0.8. Hypercube, Inc. (2009)

  28. Sastri, V.S., Bünzli, J.-C.G., Ramachandra Rao, V., Rayudu, G.V.S., Perumareddi, J.R.: Modern Aspects of Rare Earths and Their Complexes. Elsevier, Amsterdam (2003)

    Google Scholar 

  29. Liu, G.: Electronic energy level structure. In: Liu, G., Jacquier, B. (eds.) Spectroscopic Properties of Rare Earths in Optical Materials, pp. 1–94. Tsinghua University Press and Springer, Beijing and Heidelberg (2005)

    Chapter  Google Scholar 

  30. Elliott, J.P., Judd, B.R., Runciman, W.A.: Energy levels in rare-earth ions. Proc. R. Soc. (Lond.) 240, 509–523 (1957)

    Article  CAS  Google Scholar 

  31. Wong, E.Y.: Taylor series expansion of the intermediate coupling energy levels of Nd3+ and Er3+. J. Chem. Phys. 35, 544–546 (1961)

    Article  CAS  Google Scholar 

  32. Lakshman, S.V.J., Jayasankar, C.K.: Optical absorption spectrum of thulium acetate in solution. Proc. Indian Natn. Sci. Acad. 48 A, 642–653 (1982)

    Google Scholar 

  33. Davidenko, N.K., Yatsimirskii, K.B.: Regularities of band shifts in spectra of lanthanide ions upon complex formation in solutions. Theor. Exp. Chem. 6, 505–512 (1970)

    Article  Google Scholar 

  34. Yatsimirskii, K.B., Davidenko, N.K.: Absorption spectra and structure of lanthanide coordination compounds in solution. Coord. Chem. Rev. 27, 223–273 (1979)

    Article  CAS  Google Scholar 

  35. Petrov, D., Angelov, B.: Radial integrals 〈r k〉4f and nephelauxetic effect of Nd3+ in crystals. Spectrochim. Acta Part A 118, 199–203 (2014)

    Article  CAS  Google Scholar 

  36. Cotton, S.A.: Establishing coordination numbers for the lanthanides in simple complexes. C. R. Chimie 8, 129–145 (2005)

    Article  CAS  Google Scholar 

  37. Comba, P., Gloe, K., Inoue, K., Krulger, T., Stephan, H., Yoshizuka, K.: Molecular mechanics calculations and the metal ion selective extraction of lanthanoids. Inorg. Chem. 37, 3310–3315 (1998)

    Article  CAS  Google Scholar 

  38. Waber, J.T., Cromer, D.T.: Orbital radii of atoms and ions. J. Chem. Phys. 42, 4116–4123 (1965)

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. V.I. Vernadsky Institute of General and Inorganic Chemistry of the National Academy of Sciences of Ukraine, Palladina Ave. 32/34, Kiev, 03680, Ukraine

    Artem M. Mishchenko, Elena K. Trunova & Alexandra S. Berezhnytska

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  1. Artem M. Mishchenko
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  2. Elena K. Trunova
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  3. Alexandra S. Berezhnytska
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Correspondence to Artem M. Mishchenko.

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Mishchenko, A.M., Trunova, E.K. & Berezhnytska, A.S. Lanthanide Complexes with Allyl Acetoacetate in Mixed Water–Organic Media: Formation, Stability and Bonding. J Solution Chem 44, 2117–2128 (2015). https://doi.org/10.1007/s10953-015-0396-z

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