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Journal of Solution Chemistry

, Volume 42, Issue 6, pp 1123–1145 | Cite as

Solution Equilibria and Thermodynamic Studies of Complexation of Divalent Transition Metal Ions with Some Triazoles and Biologically Important Aliphatic Dicarboxylic Acids in Aqueous Media

  • M. M. Khalil
  • A. M. Radalla
  • N. M. Abd Elnaby
Article

Abstract

The formation of binary and ternary complexes of the divalent transition metal ions CuII, NiII, ZnII, and CoII with some triazoles [1,2,4-triazole (TRZ), 3-mercapto-1,2,4-triazole, and 3-amino-1,2,4-triazole], and the biologically important aliphatic dicarboxylic acids adipic, succinic, malic, malonic, maleic, tartaric, and oxalic acid, was investigated in aqueous solutions using the potentiometric technique at 25 °C and I = 0.10 mol·dm−3 NaNO3. The formation of 1:1 and 1:2 binary complexes and 1:1:1 ternary complexes was inferred from the corresponding titration curves. The formation of ternary complexes occurs in a stepwise manner with the carboxylic acids acting as primary ligands. The ionization constants (pK a) of the investigated ligands were redetermined and used for determining the stability constants of the binary and ternary complexes formed in solution. The order of stability of the ternary complexes was investigated in terms of the nature of the triazole, carboxylic acid and metal ion used. The ∆log10 K values, percent relative stabilization, and log10 X for the ternary complexes have been evaluated and discussed. The concentration distributions of the various species formed in solution were evaluated. The ionization constants of TRZ and malic acid and stability constants of their binary and ternary complexes with CuII, NiII, and CoII metal ions were studied at four different temperatures (15, 25, 35, and 45 °C) and the corresponding thermodynamic parameters have been evaluated and discussed. The complexation behavior of ternary complexes was ascertained using conductivity measurements. In addition, the formation of ternary complexes in solution has been confirmed by using UV–visible spectrophotometry.

Keywords

Triazoles Potentiometric and thermodynamic studies Stability constants Aliphatic dicarboxylic acids 

References

  1. 1.
    Sigel, H., Fisher, B.E., Prius, B.: Biological implications from the stability of ternary complexes in solution. I. Mixed-ligand complexes with manganese(II) and other 3d ions. J. Am. Chem. Soc. 99, 4489–4495 (1977)CrossRefGoogle Scholar
  2. 2.
    Bhat, A.R., Bhat, G.V., Shenoy, G.G.: Synthesis and in vitro antimicrobial activity of new 1,2,4-triazoles. J. Pharm. Pharmacol. 53, 267–272 (2001)CrossRefGoogle Scholar
  3. 3.
    Modzelewska, B.B., Jagiello, W.E., Tokarzewska, W.E.: Synthesis and biological activity of bis-1, 2, 4-triazole and bis-1, 3, 4-thiadiazole derivatives. Acta Pol. Pharm. Drug Res. 57, 199–204 (2000)Google Scholar
  4. 4.
    Kevin, T.P.: Five-membered rings with two or more nitrogen atoms. In: Katritzkv, A.R., Rees, C.W. (eds.) Comprehensive Heterocyclic Chemistry, 1st edn, pp. 785–790. Pergamon Press, Oxford (1984)Google Scholar
  5. 5.
    Kadaba, P.K.: Triazolines. 14. 1,2,3-Triazolines and triazoles. A new class of anticonvulsant. Drug design and structure activity relationships. J. Med. Chem. 31, 196–203 (1988)CrossRefGoogle Scholar
  6. 6.
    Hoffman, H.L., Ernst, E.J., Klepser, M.E.: Novel triazole antifungal agents. Expert Opin. Investig. Drugs 9, 593–605 (2000)CrossRefGoogle Scholar
  7. 7.
    Ikizler, A.A., Ikizler, A., Yüksek, H., Serdar, M: Antitumor activities of some 4.5-dihydro-1H1,2,4-triazole-5-ones. Modelling, Measurement & Control C. AMSE Press 1, 25–33 (1998)Google Scholar
  8. 8.
    Garcia, G.J.C., Mendez, R., Martin-Villacorta, J.: Determining of piperacillin and mezlocillin in human serum and urine by high-performance liquid chromatography after derivatization with 1,2,4-triazole. J. Chromatogr. A 812, 213–220 (1998)CrossRefGoogle Scholar
  9. 9.
    Colanceska-Ragenovic, K., Dimova, V., Kakurinov, V., Gabor Molnar, D., Buzarovska, A.: Synthesis, antibacterial and antifungal activity of 4-substituted-5-aryl-1,2,4-triazoles. Molecules 6, 815–824 (2001)CrossRefGoogle Scholar
  10. 10.
    Yüksek, H., Demirbas, A., Ikizler, A., Johansson, C.B., Celik, C., Ikizler, A.A.: Synthesis and antibacterial activities of some 4.5-dihydro-1H1,2,4-triazole-5-ones. Arzneim-Forsch. Drug Res. 47, 405–409 (1997)Google Scholar
  11. 11.
    Main, K.B., Martin, B.: Thermodynamics of binary and ternary complexes of 3-amino-1,2,4-triazole and amino acids with Cu(II) and Zn(II) metal ions. J. Pharmacol. 116, 3302–3310 (1995)Google Scholar
  12. 12.
    Bando, S., Ijuin, S., Hasegawa, M., Horigoshi, J.: Thermodynamics of binary and ternary complexes of 3-amino-1,2,4-triazole and amino acids with Ni(II) and Co(II) metal ions. J. Biochem. 121, 591–598 (1997)CrossRefGoogle Scholar
  13. 13.
    Gabryszewski, M.: The stability of lH-1,2,4-triazole-3-thiol and 3-amino-5-mercapto-l,2,4-triazole complexes of Co(II) and Ni(II) in aqueous solution. Pol. J. Chem. 68, 1895–1897 (1994)Google Scholar
  14. 14.
    Baraldi, M., Malavasi, W., Grandi, R.: Mercury(II) dibromo-bis-(3-amino 5-mercapto-1,2,4-triazole): synthesis, crystal structures and infrared characterization. J. Chem. Crystallogr. 26, 63–66 (1996)CrossRefGoogle Scholar
  15. 15.
    Gabryszewski, M.: Spectral and magnetic studies of the Co(II), Ni(II), Zn(II) and Cd(II) complexes with 1H–1,2,4-triazole-3-thio and 3-amino-5-mercapto-1,2,4-triazole. Spectr. Lett. 34, 57–63 (2001)CrossRefGoogle Scholar
  16. 16.
    Goel, S., Pandey, O.P., Sengupta, S.K.: Synthesis and physico-chemical studies of neodymium(II) and samarium(III) derivatives with mercaptotriazoles. Thermochim. Acta 133, 359–364 (1988)CrossRefGoogle Scholar
  17. 17.
    Nomiya, K., Tsuda, K., Kasuga, N.C.: Synthesis and X-ray characterization of helical polymer complexes [Ag(l,2,3-L) (PPh3)2]n and [Ag(l,2,4-L)(PPh3)2]n (HL = triazole) and their antimicrobial activities. J. Chem. Soc. Dalton Trans. 2, 1653–1660 (1998)Google Scholar
  18. 18.
    Gabryszewski, M.: The atability of lH-1,2,4-triazole-3-thiol and 3-amino-5-mercapto-l,2,4-triazole complexes of Co(II) and Ni(II) in aqueous solution. Pol. J. Chem. 68, 1895–1897 (1994)Google Scholar
  19. 19.
    Barszcz, B.: Complexes of Mn(II) with azoles. Part 1. Factors determining the stability of Mn(II) complexes with chosen amino derivatives of 1,2,4-triazole and pyrazole. Pol. J. Chem. 63, 9–18 (1989)Google Scholar
  20. 20.
    Gabryszewski, M.: The complexing behavior of some alkyl and amino derivatives of 1,2,4-triazole in aqueous solution. Pol. J. Chem. 66, 1067–1075 (1992)Google Scholar
  21. 21.
    Lenarcik, B., Kurdziel, K., Gabryszewski, M.: Stability and structure of transition metal complexes with azoles in aqueous solution. XXII. Complexing behavior of 1,2,4-triazole, 3-amino-1,2,4-triazole and 4-amino-l,2,4-triazole. J. Inorg. Nucl. Chem. 42, 587–592 (1980)CrossRefGoogle Scholar
  22. 22.
    Panda, S., Mishra, R., Panda, A.K., Satpathy, K.C.: Transition metal complexes with 4-amino-5-mercapto-3-methyl-1,2,4-triazole and 8-hydroxyquinoline. J. Indian Chem. Soc. 66, 472–474 (1989)Google Scholar
  23. 23.
    Reddy, M.S., Ram, K., Reddy, M.G.R.: Formation constants of binary and ternary complexes of Cu(II) with substituted 1,2,4-triazole and some O, O; O, N and N, N donors in aqueous medium. Indian J. Chem. A 28, 437–439 (1989)Google Scholar
  24. 24.
    Khalil, M.M., Mohamed, S.A., Radalla, A.M.: Potentiometric and conductometric studies on the binary and mixed-ligand complexes in solution: MII–dipicolinic acid–glycine systems. Talanta 44, 1365–1369 (1997)CrossRefGoogle Scholar
  25. 25.
    Khalil, M.M., Radalla, A.M.: Binary and ternary complexes of inosine. Talanta 46, 53–61 (1998)CrossRefGoogle Scholar
  26. 26.
    Khalil, M.M., Attia, A.E.: Potentiometric studies on the binary and ternary complexes of copper(II) containing dipicolinic acid and amino acids. J. Chem. Eng. Data 44, 180–184 (1999)CrossRefGoogle Scholar
  27. 27.
    Khalil, M.M.: Complexation equilibria & determination of stability constants of binary and ternary complexes with ribonucleotides (AMP, ADP, and ATRP) and salicylhydroxamic acid as ligands. J. Chem. Eng. Data 45, 70–74 (2000)CrossRefGoogle Scholar
  28. 28.
    Khalil, M.M.: Solution equilibria & stabilities of binary and ternary complexes with N-(2-acetamido)iminodiacetic acid and ribonucleotides (AMP, ADP, and ATP). J. Chem. Eng. Data 45, 837–840 (2000)CrossRefGoogle Scholar
  29. 29.
    Khalil, M.M., Attia, A.E.: Potentiometric studies on the formation equilibria of binary and ternary complexes of some metal ions with dipicolinic acid and amino acids. J. Chem. Eng. Data 45, 1108–1110 (2000)CrossRefGoogle Scholar
  30. 30.
    Khalil, M.M., Taha, M.: Equilibrium studies of binary and ternary complexes involving tricine and some selected amino acids. Monatsch. Chem. 135, 385–395 (2004)CrossRefGoogle Scholar
  31. 31.
    Khalil, M.M., Fazary, A.E.: Potentiometric studies on binary and ternary complexes of di- and trivalent metal ions involving some hydroxamic acids, amino acids, and nucleic acid components. Monatsch. Chem. 135, 1455–1474 (2004)CrossRefGoogle Scholar
  32. 32.
    Khalil, M.M., El-Deeb, M.M., Mahmoud, R.K.: Equilibrium studies of binary systems involving lanthanide and actinide metal ions and some selected aliphatic and aromatic monohydroxamic acids. J. Chem. Eng. Data 52, 1571–1579 (2007)CrossRefGoogle Scholar
  33. 33.
    Khalil, M.M., Mahmoud, R.K.: New insights into M(II)–hydroxamate interactions: the electro-analytical behavior of metal(II) complexes involving monohydroxamic acids and diamines in an aqueous medium. J. Chem. Eng. Data 53, 2318–2327 (2008)CrossRefGoogle Scholar
  34. 34.
    Khalil, M.M., Radalla, A.M., Mohamed, A.G.: Potentiometric investigation on complexation of divalent transition metal ions with some zwitterionic buffers and triazoles. J. Chem. Eng. Data 52, 3261–3272 (2009)CrossRefGoogle Scholar
  35. 35.
    Grans, G.: Determination of the equivalence point in potentiometric titration. Analyst 77, 661–667 (1952)CrossRefGoogle Scholar
  36. 36.
    Welcher, F.J.: The Analytical Uses of Ethylenediaminetetraacetic Acid. Von Nostrand, Princeton, NJ (1965)Google Scholar
  37. 37.
    Grans, P., O’Sullivan, B.: Glee, a new computer program for glass pH-electrode calibration. Talanta 51, 33–37 (2000)CrossRefGoogle Scholar
  38. 38.
    Longhi, P., D’Andrea, F., Mussini, P.R., Mussini, T., Rondinini, S.: Verification of the approximate equitransference of the aqueous potassium chloride salt bridge at high concentrations. Anal. Chem. 62, 1019–1021 (1990)CrossRefGoogle Scholar
  39. 39.
    Izutsu, K., Muramatsu, M., Aoki, Y.: Liquid junction potential between different solvents: a junction with different electrolytes on the two sides. J. Electroanal. Chem. 338, 125–132 (1992)CrossRefGoogle Scholar
  40. 40.
    Brandariz, I., Barriada, J.L., Taboada-Pan, C., Sastre de Vicente, M.E.: Estimating the change in liquid junction potential on glass electrodes. Electroanalysis 13, 1110–1114 (2001)CrossRefGoogle Scholar
  41. 41.
    Irving, H.M., Rossotti, H.S.: Methods for computing successive stability constants from experimental formation curves. J. Chem. Soc. 3397–3405 (1953)Google Scholar
  42. 42.
    Irving, H.M., Rossotti, H.S.: The calculation of formation curves of metal complexes from pH titration curves in mixed solvent. J. Chem. Soc. 2904–2913 (1954)Google Scholar
  43. 43.
    Lenarcik, B., Kurdziel, K., Gabryszewski, M.: Stability and structure of transition metal complexes with azoles in aqueous solution. XXII. Complexing behavior of 1,2,4-triazole, 3-amino-1,2,4-triazole and 4-amino-l,2,4-triazole. J. Inorg. Nucl. Chem. 42, 587–592 (1980)CrossRefGoogle Scholar
  44. 44.
    Catalan, J., Menendez, M., Elguero, J.: On the relationship between basicity and acidity in azoles. Bull. Soc. Chim. Fr. 94, 30–33 (1985)Google Scholar
  45. 45.
    Weast, R. (ed.): Handbook of Chemistry and Physics, 68th edn. CRC press, Boca Raton, FL (1987)Google Scholar
  46. 46.
    Inezedy, J.: Determination of equilibrium constants. In: Ellis, S. (ed.) Analytical Applications of Complex Equilibria. Ellis Howard, Chichester, UK (1967) Google Scholar
  47. 47.
    Smith, R.M., Martell, A.E.: NIST critically selected stability constants of metal complexes database, Version 3.0. NIST Standard Reference Database 46, U.S. Department of Commerce, National Institute of Standard and Technology (1997)Google Scholar
  48. 48.
    Radalla, A.M.: Studies on complexation of resorcinol with some divalent transition metal ions and aliphatic dicarboxylic acids in aqueous media. J. Solution Chem. 39, 1394–1404 (2010)CrossRefGoogle Scholar
  49. 49.
    Irving, H., Williams, R.P.: Reversion: a new procedure in absorptiometry. Nature (London) 30, 162–746 (1948) Google Scholar
  50. 50.
    Laurie, S.H., James, C.: Binary and ternary complexes of hydroxamic acids. Inorg. Chim. Acta 78, 225–229 (1983)CrossRefGoogle Scholar
  51. 51.
    Gans, P., Vacca, A.: Application of the Davidon–Fletcher–Powell method to the calculation of stability constants. Talanta 21, 45–51 (1974)CrossRefGoogle Scholar
  52. 52.
    Sanaie, N., Hayres, C.A.: Formation constants and coordination thermodynamics for binary and ternary complexes of copper(II), l-hydroxyproline, and an amino acid enantiomer. J. Chem. Eng. Data 50, 1848–1856 (2005)CrossRefGoogle Scholar
  53. 53.
    Offiong, O.E.: Formation constants and thermodynamic parameters of α-pyridoin thiosemicarbazones with divalent metal ions. Trans. Met. Chem. 23, 553–556 (1998)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2013

Authors and Affiliations

  • M. M. Khalil
    • 1
  • A. M. Radalla
    • 1
  • N. M. Abd Elnaby
    • 1
  1. 1.Department of Chemistry, Faculty of ScienceBeni-Suef UniversityBeni-SuefEgypt

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