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Complexing Properties of Pyridine-4-methylene Derivatives: Diethyl(pyridine-4-ylmethyl)phosphate, 4-Pyridylmethylphosphonic Acid and 4-Hydroxymethylpyridine with Cu(II) in Aqueous Solution

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Abstract

The coordinating properties in aqueous solution of two novel pyridine-4-methylene derivatives, diethyl(pyridine-4-ylmethyl)phosphate (4-PO(Oet)2CH2-py = 4-pmOpe) and 4-pyridylmethylphos phonic acid (4-PO(OH)2CH2-py = 4-pmpa), towards Cu(II) are compared with those of 4-hydroxymethyl-pyridine (4-OHCH2-py = 4-pmOH). The two new derivatives were chosen due to their expected interesting biological activity that is observed for related solid complexes of several metals with various pyridine-methylene derivatives. The studies were carried out using pH potentiometry, UV–Vis spectrophotometry and EPR spectroscopy. The results show that 4-pmOpe and 4-pmpa, similarly to 4-OHCH2-py, form mononuclear L:M = 1:1 and 2:1 complexes with Cu(II). However, in the case of 4-pmpa, complexation occurs both via oxygen atoms of the R-\( {\text{PO}}_{3}^{2 - } \) group (ML and ML2 species) and the N(1) nitrogen (protonated MLH and ML2H2 complexes). The possible attendance of the third ligand in the coordination sphere was indicated for 4-OHCH2-py by EPR spectroscopy.

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References

  1. Sigel, H., Kapinos, L.E.: Quantification of isomeric equilibria for metal ion complexes formed in solution by phosphate or phosphonate ligands with a weakly coordinating second site. Coord. Chem. Rev. 200–202, 563–594 (2000)

    Article  Google Scholar 

  2. Galezowska, J., Gumienna-Kontecka, E.: Phosphonates, their complexes and bio-applications: a spectrum of surprising diversity. Coord. Chem. Rev. 256, 105–124 (2012)

    Article  CAS  Google Scholar 

  3. Temperini, C., Innocenti, A., Guerri, A., Scozzafava, A., Rusconi, S., Supuran, C.T.: Phosph(on)ate as a zinc-binding group in metalloenzyme inhibitors: X-ray crystal structure of the antiviral drug foscarnet complexed to human carbonic anhydrase I. Bioorg. Med. Chem. Lett. 17, 2210–2215 (2007)

    Article  CAS  Google Scholar 

  4. Kalinowska, U., Matławska, K., Chęcińska, L., Domagała, M., Kontek, R., Osiecka, R., Ochocki, J.: Synthesis, spectroscopy and antiproliferative activity of cis- and trans-platinum(II) complexes with diethyl(pyridin-4-ylmethyl)phosphate. X-ray crystal structure of trans-Pt(II) complex. J. Inorg. Biochem. 99, 2024–2031 (2005)

    Article  CAS  Google Scholar 

  5. Kalinowska, U., Chęcińska, L., Małecka, M., Erxleben, A., Lippert, B., Ochocki, J.: Synthesis and spectroscopy of diethyl(pyridinylmethyl)phosphates and their palladium(II) complexes: X-ray crystal structures of Pd(II) complexes. Inorg. Chim. Acta 358, 2464–2472 (2005)

    Article  CAS  Google Scholar 

  6. Kalinowska-Lis, U., Szmigiero, L., Studzian, K., Ochocki, J.: Cytotoxic activity and chemical reactivity of cis-platinum(II) and trans-palladium(II) complexes with diethyl(pyridinylmethyl)phosphates. Eur. J. Med. Chem. 44, 660–664 (2009)

    Article  CAS  Google Scholar 

  7. Żurowska, B., Ochocki, J., Białońska, A., Kalinowska-Lis, U.: Spectroscopic studies and crystal structure of a dimeric Zn(II) complex with diethyl(pyridin-2-ylmethyl)phosphate. J. Coord. Chem. 63, 3764–3771 (2010)

    Article  Google Scholar 

  8. Żurowska, B., Ślepokura, K., Lis, T., Ochocki, J.: Different crystal forms of Zn(II) compound with diethyl(pyridin-3-ylmethyl)phosphonate (3-pmpe) ligand: Zn(3-pmpe)Cl2. Inorg. Chim. Acta 362, 733–738 (2009)

    Article  Google Scholar 

  9. Żurowska, B., Kalinowska-Lis, U., Białońska, A., Ochocki, J.: Coordination properties of diethyl(pyridin-2-ylmethyl)phosphate (2-pmOpe) ligand with perchlorate transition metal salts: crystal structure of [Co(2-pmOpe)2(H2O)2](ClO4)2. J. Mol. Struct. 889, 98–103 (2008)

    Article  Google Scholar 

  10. Kalinowska-Lis, U., Żurowska, B., Ślepokura, K., Ochocki, J.: Coordination properties of ethyl bis(pyridin-2-ylmethyl)phosphate ligand with copper and zinc chloride. X-ray crystal structure of Cu(II) complex. Inorg. Chim. Acta 376, 18–22 (2011)

    Article  CAS  Google Scholar 

  11. Żurowska, B., Kalinowska-Lis, U., Brzuszkiewicz, A., Ochocki, J.: Spectroscopic and magnetic properties of diethyl(pyridin-4-ylmethyl)phosphate (4-pmOpe) ligand with perchlorate transition metal salts. Crystal structure of [Cu(4-pmOpe)2(ClO4)2]. Inorg. Chim. Acta 362, 1435–1440 (2009)

    Article  Google Scholar 

  12. Kalinowska-Lis, U., Żurowska, B., Ochocki, J.: Spectroscopic and magnetic evidence of coordination properties of bioactive diethyl(pyridin-4-ylmethyl)phosphate ligand with chloride transition-metal ions. Chem. Pap. 65, 660–666 (2011)

    Article  CAS  Google Scholar 

  13. Chruścinski, L., Młynarz, P., Malinowska, K., Ochocki, J., Boduszek, B., Kozłowski, H.: Methylphosphonate, hydroxymethylphosphonate and aminomethylphosphonate ligands containing pyridine, pyrazole or imidazole side chains: the coordination abilities towards Cu(II) ions. Inorg. Chim. Acta 303, 47–53 (2000)

    Article  Google Scholar 

  14. Kostka, K., Ochocki, J.: Phosphonic complexones. Part II. Synthesis, thermal and spectroscopic analysis and investigation on protolytic equilibria of 4-pyridylmethylphosphonic acid (4-pmpa) and 2-quinolylmethylphosphonic acid (2-qmpa). Pol. J. Chem. 61, 177–188 (1987)

    CAS  Google Scholar 

  15. Maruszewska-Wieczorkowska, E., Michalski, J.: Alkyl and alkenyl pyridines. Part IX. Phosphonate and tertiary phosphine oxides containing 2- and 4-pyridylmethyl groups at the phosphorus atom, and some of their reactions. Rocz. Chem. 38, 625–633 (1964)

    CAS  Google Scholar 

  16. Irving, H., Miles, M.G., Pettit, L.D.: A study of some problems in determining the stoichiometric proton dissociation constants of complexes by potentiometric titrations using a glass electrode. Anal. Chim. Acta 38, 475–485 (1967)

    Article  CAS  Google Scholar 

  17. Gans, P., Sabatini, A., Vacca, A.: SUPERQUAD: an improved general program for computation of formation constants from potentiometric data. J. Chem. Soc. Dalton Trans. 6, 1195–1200 (1985)

    Article  Google Scholar 

  18. Gans, P., Sabatini, A., Vacca, A.: Investigation of equilibria in solution. Determination of equilibrium constants with the HYPERQUAD suite of programs. Talanta 43, 1739–1753 (1996)

    Article  CAS  Google Scholar 

  19. Alderighi, L., Gans, P., Ienco, A., Peters, D., Sabatini, A., Vacca, A.: Hyperquad simulation and speciation (HySS): a utility program for the investigation of equilibria involving soluble and partially soluble species. Coord. Chem. Rev. 184, 311–318 (1999)

    Article  CAS  Google Scholar 

  20. Kiss, T., Lázár, I.: Structure and stability constants of metal complexes in solution. In: Kukhar, V.P., Hudson, H.R. (eds.) Aminophosphonic and aminophosphinic acids: chemistry and biological activity, pp. 286–325. Wiley, Chichester (2000)

    Google Scholar 

  21. Kufelnicki, A., Kupińska, I., Jezierska, J., Ochocki, J.: Complexes of uracil (2,4-dihydroxypyrimidine) derivatives. Part I. Cu(II), Ca(II) and Mg(II) coordination with uracil and related compounds in aqueous solution. Pol. J. Chem. 76, 1559–1570 (2002)

    CAS  Google Scholar 

  22. Kufelnicki, A., Woźniczka, M., Kalinowska-Lis, U., Jezierska, J., Ochocki, J.: Synthesis, acid–base and complexing properties with Cu(II), Co(II) and Zn(II) in aqueous solution of a novel 1H-benzimidazol-2-ylmethyl diethyl phosphate ligand: comparison with other 2-substituted benzimidazole ligands. Polyhedron 53, 20–25 (2013)

    Article  CAS  Google Scholar 

  23. Kulig, J., Lenarcik, B., Rzepka, M.: Potentiometric studies on complexes of silver(I) in solutions: 5: relationship between stability-constants of Ag(I) complexes of pyridine-derivatives and Hammett omicron-coefficients. Pol. J. Chem. 61, 59–68 (1987)

    CAS  Google Scholar 

  24. Sun, M.S., Brewer, D.G.: Comparative formation constants for complexes of copper, nickel, and silver with some substituted pyridines. Can. J. Chem. 45, 2729–2739 (1967)

    Article  CAS  Google Scholar 

  25. Barańska, M., Chruszcz, K., Małek, K., Kulinowska, J., Proniewicz, L.M.: Vibrational and quantum-chemical study of pH dependent molecular structures of (hydroxypyridin-4-yl-methyl)phosphonic acid. Vib. spectrosc. 33, 83–92 (2003)

    Article  Google Scholar 

  26. Kulig, J., Lenarcik, B., Rzepka, M.: Stability and structure of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes of pyridine-derivatives. 10. Application of Hammett’s equation in complexation of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with pyridine-derivatives. Pol. J. Chem. 61, 735–745 (1987)

    CAS  Google Scholar 

  27. Odani, A., Masuda, H., Inukai, K., Yamauchi, O.: Pteridine-containing ternary and quaternary complexes as models for metalloenzyme-pterin cofactor-substrate association. Structure of ternary copper(II)-2,2′-bipyridine-lumazine complex and successful equilibrium study of a quaternary copper(II) system. J. Am. Chem. Soc. 114, 6294–6300 (1992)

    Article  CAS  Google Scholar 

  28. Powell, K.J., Brown, P.L., Byrne, R.H., Gajda, T., Hefter, G., Sjöberg, S., Wanner, H.: Chemical speciation of environmentally significant metals with inorganic ligands. Part 2: the Cu2+–OH−, Cl−, CO3 2−, SO4 2−, and PO4 3− systems. Pure Appl. Chem. 79, 895–950 (2007)

    Article  CAS  Google Scholar 

  29. Kapinos, L.E., Sigel, H.: Acid–base and metal ion binding properties of pyridine-type ligands in aqueous solution: effect of ortho substituents and interrelation between complex stability and ligand basicity. Inorg. Chim. Acta 337, 131–142 (2002)

    Article  CAS  Google Scholar 

  30. Sigel, H., McCormick, D.B.: On the discriminating behavior of metal ions and ligands with regard to their biological significance. Acc. Chem. Res. 3, 201–208 (1970)

    Article  CAS  Google Scholar 

  31. Sigel, R.K.O., Sigel, H.: Complex formation of nickel(II) with sugar residues, nucleobases, phosphates, nucleotides, and nucleic acids in: nickel and its surprising impact in nature. Met. Ions Life Sci. 2, 109–180 (2007)

    CAS  Google Scholar 

  32. Brown, H.C., Mihm, X.R.: Steric effects in displacement reactions. III. The base strengths of pyridine, 2,6-lutidine and the monoalkylpyridines. J. Am. Chem. Soc. 77, 1723–1726 (1955)

    Article  CAS  Google Scholar 

  33. Lever, A.B.P.: Inorganic Electronic Spectroscopy, p. 355. Elsevier, Amsterdam (1968)

    Google Scholar 

  34. Lever, A.B.P.: Inorganic Electronic Spectroscopy, 2nd edn, p. 560. Elsevier, Amsterdam (1984)

    Google Scholar 

  35. Vishnevskaya, G.P., Safin, R.S., Kargman, V.B., Kopylova, V.D., Fedstova, M.A., Galitskaya, N.B.: Structure and sorption properties of vinylpyridine ion exchangers of different hydrophilic nature, containing copper and silver, based on EPR data. Theor. Exp. Chem. 26, 439–444 (1990)

    Article  Google Scholar 

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Acknowledgments

This work was partially supported by the Polish Ministry of Science and Higher Education (Grant No. N405 303236) and by the Medical University of Łódź {Statute Fund No. 503/3-016-02/503-01 (J. Ochocki) and Statute Fund No. 503/3-014-02/503-01 (A. Kufelnicki)}. J. Jezierska is grateful to the Ministry of Science and Higher Education of the Republic of Poland for a financial subsidy aimed at statutory activity of the Faculty of Chemistry, University of Wrocław.

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Authors and Affiliations

  1. Department of Physical and Biocoordination Chemistry, Faculty of Pharmacy, Medical University of Łódź, Muszyńskiego 1, 90-151, Łódź, Poland

    Aleksander Kufelnicki, Mirosława Świątek & Magdalena Woźniczka

  2. Department of Bioinorganic Chemistry, Faculty of Pharmacy, Medical University of Łódź, Muszyńskiego 1, 90-151, Łódź, Poland

    Urszula Kalinowska-Lis & Justyn Ochocki

  3. Faculty of Chemistry, University of Wrocław, F. Joliot-Curie 14, 50-383, Wrocław, Poland

    Julia Jezierska

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  1. Aleksander Kufelnicki
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Correspondence to Aleksander Kufelnicki.

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Kufelnicki, A., Świątek, M., Woźniczka, M. et al. Complexing Properties of Pyridine-4-methylene Derivatives: Diethyl(pyridine-4-ylmethyl)phosphate, 4-Pyridylmethylphosphonic Acid and 4-Hydroxymethylpyridine with Cu(II) in Aqueous Solution. J Solution Chem 45, 28–41 (2016). https://doi.org/10.1007/s10953-015-0424-z

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