Abstract
In this study the binary and ternary complexes of copper(II) with substituted 1,10-phenanthrolines [s-phen: 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (dmphen) and 5-nitro-1,10-phenanthroline (nphen)] and l-amino acids [aa: l-phenylalanine (phe), l-tyrosine (tyr) and l-tryptophan (trp)] have been investigated using potentiometric methods in 0.1 mol·L−1 KCl aqueous ionic media at 298.2 K. The protonation constants of the ligands and the stability constants of the binary and ternary complexes of Cu(II) with the ligands were calculated from the potentiometric data using the “BEST” software package. It was inferred that the aromatic 1,10-phenanthrolines act as a primary ligand in the ternary complexes, while the oxygen and nitrogen donor-containing amino acids are secondary ligands. The observed values of Δlog10 K indicate that the ternary complexes are more stable than the binary ones, suggesting no interaction takes place between the ligands in the ternary complexes. The magnitudes of the measured stability constants of all of the ternary complexes are in the order [Cu(s-phen)(trp)]+ > [Cu(s-phen)(tyr)]+ > [Cu(s-phen)(phe)]+, which is identical to the sequence found for the binary complexes of Cu(II) with the amino acids. When the substituted 1,10-phenanthroline is changed, the stability constants of the ternary complexes decrease in the following order: [Cu(dmphen)(aa)]+ > [Cu(phen)(aa)]+ > [Cu(nphen)(aa)]+.
Similar content being viewed by others
References
May, P.M., Williams, D.R.: In: Sigel, H. (ed.) Metal Ions in Biological Systems Properties of Copper, vol. 12. Marcel Dekker, New York (1981)
Sigel, H. (ed.): Metal Ions in Biological Systems, vol. 13. Marcel Dekker, New York (1981)
Miura, T., Hori-J, A., Mototani, H., Takeuchi, H.: Raman spectroscopic study on the copper(II) binding mode of prion octapeptide and its pH dependence. Biochemistry 38, 11560–11569 (1999)
Ramakrishnan, S., Rajendiran, V., Palaniandavar, M., Periasamy, V.S., Srinag, B.S., Krishnamurthy, H., Akbarsha, M.A.: Induction of cell death by ternary copper(II) complexes of l-tyrosine and diimines: role of coligands on DNA binding and cleavage and anticancer activity. Inorg. Chem. 48, 1309–1322 (2009)
Remko, M., Fitz, D., Broer, R., Rode, B.M.: Effect of metal Ions (Ni2+, Cu2+ and Zn2+) and water coordination on the structure of l-phenylalanine, l-tyrosine, l-tryptophan and their zwitterionic forms. J. Mol. Model. 17, 3117–3128 (2011)
Devi, K.V.S., Raju, B.R., Rao, G.N.: Effect of dielectric constant on protonation equlibria of L-dopa and 1,10-phenanthroline in dioxan–water mixtures. Acta Chim. Slov. 57, 398–404 (2010)
Daniele, P.G., Rigano, C., Sammartano, S.: Ionic strength dependence of formation constants–V: protonation constants of some nitrogen-containing ligands at different temperatures and ionic strengths. Talanta 32, 78–80 (1985)
Capone, S., Robertis, A.D., Stefano, C.D., Scarcella, R.: Thermodynamics of formation of magnesium, calcium, strontium and barium complexes with 2,2′-bipyridyl and 1,10-phenanthroline, at different ionic strengths in aqueous solution. Talanta 32, 675–677 (1985)
Robertis, A.D., Foti, C., Gianguzza, A., Rigano, C.: Protonation thermodynamics of 1,10-phenanthroline in aqueous solution. Salt effects and weak complex formation. J. Solution Chem. 25, 597–606 (1996)
Bandyopadhyay, S., Mandal, A.K., Aditya, S.: Thermodynamics of 2,2′-dipyridinium ion and 1,10-phenanthrolinium ion in tert-butanol–water and glycerol–water media at 25. J. Indian Chem. Soc. 58, 467–473 (1981)
Bandyopadhyay, S., Mukherjee, G.N., Drew, M.G.B.: Equilibrium studies on mixed ligand complex formation of Co(II), Ni(II), Cu(II) and Zn(II) with N-(2-hydroxybenzyl)-l-histidine(H2hb-L-his) and typical N, N donor ligands: crystal structure of [Ni(hb-L-his) (bipyridine)] H2O complex. Inorg. Chim. Acta 359, 3243–3251 (2006)
Eun-Jun, G., Xia, L., Qi-Tao, L.: Study on electronic effect and aromatic ring stacking of Pd(II)–aromatic diamine–aminoacid ternary complexes. Chinese J. Inorg. Chem. 18, 442–446 (2002)
Brisbin, D.A., McBryde, W.A.E.: The stability of metallic complexes of two dimethyl-phenanthrolines. Can. J. Chem. 41, 1135–1141 (1963)
Yasuda, M., Sone, K., Yamasaki, K.: Stability of zinc and cadmium complexes with some methyl derivatives of 1,10-phenanthroline and 2,2′-bipyridine. J. Am. Chem. Soc. 60, 1667–1668 (1956)
Brandt, W.W., Gullstrom, D.K.: Studies on some ferrous complexes of substituted 1,10-phenanthrolines. J. Am. Chem. Soc. 74, 3532–3535 (1952)
Banks, C.V., Bystroff, R.I.: Stability orders in transition metal-1,10-phenanthroline complexes. J. Am. Chem. Soc. 81, 6153–6158 (1959)
Köseoğlu, F., Kılıç, E., Doğan, A.: Studies on protonation constants and solvation of α-amino acids in dioxan–water mixtures. Anal. Biochem. 277, 243–246 (2000)
Demirelli, H., Köseoğlu, F.: Eqilibrium studies of Schiff bases and their complexes with Cu(II), Ni(II) and Zn(II) derived from salicylaldehyde and some α-amino acids. J. Solution Chem. 34, 561–577 (2005)
Correia, I., Marcão, S., Koci, K., Tomaz, I., Adão, P., Kiss, T., Jakusch, T., Avecilla, F., Pessoa, J.C.: Vanadium(IV) and -(V) complexes of reduced Schiff bases derived from aromatic o-hydroxyaldehydes and tyrosine derivatives. Eur. J. Inorg. Chem. 2011, 694–708 (2011)
Dallavalle, F., Folesani, G., Sabatini, A., Tegoni, M., Vacca, A.: Formation equilibria of ternary complexes of copper(II) with (S)-tryptophanhydroxamic acid and both D- and L-amino acids in aqueous solution. Polyhedron 20, 103–109 (2001)
Podsiadły, H., Karwecka, Z.: Complexes of vanadium(III) with aromatic amino acids and l-proline in aqueous solution. Polyhedron 28, 1568–1572 (2009)
Krishnamoorthy, C.R., Sunil, S., Ramalingam, K.: The effect of ligand donor atoms on ternary complex stability. Polyhedron 8, 1451–1456 (1985)
Kholeif, S., Anderegg, G.: Equilibrium studies of aspartame and some of its degradation products with hydrogen(I) and copper(II) under physiological conditions using potentiometric pH measurements. Inorg. Chim. Acta 257, 225–230 (1997)
Molchanov, A.S., Ledenkov, S.F.: Effect of a water–ethanol solvent on the stability of copper(II) complexes with l-tyrosine. Rus. J. Gen. Chem. 80, 219–222 (2010)
Mohan, A., Yogi, D.S., Kumar, G.N., Mohan, M.S.: Influence of electronic, steric and stacking interactions in ternary Ni(II) and Cu(II) complexes containing 2,2′,2′’-terpyridine and a series of amino acids. Indian J. Chem. 32A, 785–788 (1993)
Yamauchi, O., Odani, A.: Structure-stability relationship in ternary copper(II) complexes involving aromatic amines and tyrosine or related amino acids. ıntramolecular aromatic ring stacking and its regulation through tyrosine phosphorylation. J. Am. Chem. Soc. 107, 5938–5945 (1985)
Aydın, R., Yırıkoğulları, A.: Potentiometric study on complexation of divalent transition metal ions with amino acids and adenosine 5′-triphosphate. J. Chem. Eng. Data 55, 4794–4800 (2010)
Aydin, R., Serbest, Z., Özer, U.: Formation of the complexes between lanthanum(III) ion and 5-sulfosalicylate, 5-nitrosalicylate. Rev. Inorg. Chem. 25, 271–283 (2005)
Aydin, R.: Study on the interaction of yttrium(III) with adrenaline, noradrenaline, and dopamine. J. Chem. Eng. Data 52, 2400–2404 (2007)
Aydin, R., İnci, D.: Potentiometric and spectrophotometric studies of the complexation of lanthanum(III) with adrenaline, noradrenaline, and dopamine. J. Chem. Eng. Data 57, 967–973 (2012)
Martell, A.E., Motekaites, R.J.: Determination and Use of Stability Constants. VCH Publishers, New York (1989)
Gran, G.: Determination of the equivalent point in potentiometric titrations. Acta Chem. Scand. 4, 559–577 (1950)
Rossotti, F.J.C., Rossotti, H.: Potentiometric titrations using gran plots. J. Chem. Educ. 42, 375–378 (1965)
Schwarzenbach, G., Flaschka, A.: Complexometric Titrations. Methuen, New York (1969)
Patel, P.J., Patel, V.K., Bhattachanya, P.K.: Effect of two ligands on ternary complex stability. Inorg. Chem. 21, 3163–3166 (1982)
Griesser, H., Sigel, H.: Ternary complexes in solution. VIII. Complex formation between the copper(II)-2,2′-bipyridyl l:1 complex and ligands containing oxygen and/or nitrogen as donor atoms. Inorg. Chem. 9, 1238–1242 (1970)
Acknowledgments
We thank the Research Fund of Uludag University for financial support given to this research project (Project Number UAP(F)-2011/71). This study is a part of MS thesis of the first author accepted on 16 January 2013 by the Graduate School of Natural and Applied Sciences of Uludag University.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
İnci, D., Aydın, R. Stabilities of the Ternary Complexes of Copper(II) with Substituted 1,10-Phenanthrolines and Some Amino Acids in Aqueous Solution. J Solution Chem 43, 711–726 (2014). https://doi.org/10.1007/s10953-014-0157-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10953-014-0157-4