Abstract
Seven-coordinate Fe(EDTA)–L complexes, where L represents a DNA constituent (uracil, uridine, thymine, thymidine and inosine), methylamine, ammonium chloride or imidazole, were investigated to resolve the solution chemistry of this system. The results show formation of 1:1 complexes with DNA constituents and the other ligands, supporting the hepta-coordination mode of Fe(III) ion. Stability constants of the complexes were measured by potentiometric titration at 25 °C and ionic strength 0.1 mol⋅L−1 NaNO3. The hydrolysis constant of [Fe(EDTA)(H2O)]− and the formation constants of the complexes formed in solution were calculated using the non-linear least-squares program MINIQUAD-75. The concentration distributions of the various complex species were evaluated as a function of pH. The thermodynamic parameters ΔH 0 and ΔS 0, calculated from the temperature dependence of the equilibrium constants, were determined for the Fe(EDTA)–uracil complex. The effect of dioxane as a solvent on the protonation constant of uracil, hydrolysis constants of [Fe(EDTA)(H2O)]−, and the formation constants of the Fe(EDTA)–uracil complex are discussed.
Similar content being viewed by others
References
Ali, M.A., Mirza, A.H., Chartres, J.D., Bernhardt, P.V.: Synthesis, characterization and X-ray crystal structures of seven-coordinate pentagonal–bipyramidal zinc(II), cadmium(II) and tin(IV) complexes of a pentadentate N3S2 thiosemicarbazone. Polyhedron 30, 299–306 (2011)
Salvemini, D., Riley, D.P., Cuzzocrea, S.: SOD mimitics are coming of age. Nat. Rev., Drug Discov. 1, 367–374 (2002)
Muscoli, C., Cuzzocrea, S., Riley, D.P., Zweier, J.L., Thiemermann, C., Wang, Z.-Q., Salvemini, D.: On the selectivity of superoxide dismutase mimetics and its importance in pharmacological studies. Br. J. Pharmacol. 140, 445–460 (2003)
Ivanović-Burmazović, I., Hamaza, M.S.A., van Eldik, R.: Substitution behaviour of an unusual seven-coordinate iron(III) complex in different solvents. Inorg. Chem. Commun. 5, 937–940 (2002)
Ivanović-Burmazović, I., Hamza, M.S.A., van Eldik, R.: A detailed mechanistic study of the substitution behavior of unusual seven-coordinate iron(III) complex in aqueous solution. Inorg. Chem. 41, 5150–5161 (2002)
Hoard, J.L., Lind, M., Silverton, J.V.: The stereochemistry of aquo[ethylenediaminetetrataacetato] ferrate(III) ion. J. Am. Chem. Soc. 83, 2770–2771 (1961)
Brausen, A., van Eldik, R.: Further mechanistic information on the reaction between FeIII(EDTA) and hydrogen peroxide: observation of a second reaction step and importance of pH. Inorg. Chem. 43, 5351–5359 (2004)
López-Alcalá, J.M., Puerta-Vizcáıno, M.C., Gonźalez-Vílchez, F.: A redetermination of sodium aqua [ethylenediaminetetrataacetato]ferrate(III)dihydrate, Na[Fe(C10H12N2O8(H2O))]⋅2H2O. Acta Crystallogr. Sect. C 40, 939–941 (1984)
Solans, X., Altaba, M.F., Garcia-Oricain, J.: Crystal structure of ethylenediaminetetrataacetato metal complexes. VII. Structures containing the [Fe(C10H12N2O8(H2O)]− anion: ethylene diammonium (EDA) and tetraethyl ammonium (TEA) salts. Acta Crystallogr. Sect. C 40, 635–638 (1984)
Lambert, J.L., Godsey, Ch.E., Setz, L.M.: Preparation and photodecomposition of the complex acid, hydrogen aqua ethylenediaminetetrataacetatoferrate(III). Inorg. Chem. 2, 127–129 (1963)
Ivanović-Burmazović, I., Hamaza, M.S.A., van Eldik, R.: Solvent tuning of the substitution behavior of a seven-coordinate iron(III) complex. Inorg. Chem. 45, 1575–1584 (2006)
El-Sherif, A.A., Shoukry, M.M., El-Bahnasawy, R.M., Ahmed, D.M.: Complex formation reactions of palladium(II)–1,3-diaminopropane with various biologically relevant ligands. Kinetics of hydrolysis of glycine methyl ester through complex formation. Cent. Eur. J. Chem. 8, 919–927 (2010)
El-Sherif, A.A., Shoukry, M.M.: Ternary copper(II) complexes involving 2-aminomethyl-benzimidazole and some bio-relevant ligands. Equilibrium studies and kinetics of hydrolysis for glycine methyl ester under complex formation. Inorg. Chim. Acta 360, 473–487 (2007)
El-Sherif, A.A.: Mixed ligand complex formation reactions and equilibrium studies of Cu(II) with bidentate heterocyclic alcohol (N, O) and some bio-relevant ligands. J. Solution Chem. 39, 131–150 (2010)
El-Sherif, A.A.: Coordination properties of bidentate (N, O) and tridentate (N, O, O) heterocyclic alcohols with dimethyltin(IV) ion. J. Coord. Chem. 64, 1240–1253 (2011)
Van Uitert, G.L., Hass, C.G.: Studies on the coordination compounds. A method for determining thermodynamic equilibrium constants in mixed solvents. J. Am. Chem. Soc. 75, 451–455 (1971)
Motekaitis, R.J., Martell, A.E., Nelson, D.A.: Formation and stabilities of cobalt(II) chelates of N-benzyl triamine Schiff bases and their dioxygen complexes. Inorg. Chem. 23, 275–283 (1984)
Alousi, A.S., Shehata, M.R., Shoukry, M.M., Mohamed, N.M.: Interaction of dimethyltin(IV) and trimethyltin(IV) with dehydroacetic acid. J. Chem. Speciat. Bioavailab. 21, 1–6 (2009)
Gans, P., Sabatini, A., Vacca, A.: An improved computer program for the computation of formation constants from potentiometric data. Inorg. Chim. Acta 18, 237–239 (1976)
Pettit, L.: University of Leeds, UK. The program species downloaded from internet site of Academic Soft Co., UK. http://www.acadsoft.co.uk/scdbase.htm (1999)
Perrin, D.D.: Stability Constants of Metal-Ion Complexes: Part B. Organic Ligands. Pergamon, Oxford (1999)
Maskos, K.: The interaction of metal ions with nucleic acids. A nuclear magnetic resonance relaxation time study of the copper(II)–inosine 5′-monophosphate system in solution. Acta Biochem. Pol. 28, 183–200 (1981)
Maskos, K.: Spectroscopic studies on the copper(II)–inosine system. J. Inorg. Biochem. 25, 1–14 (1985)
Martin, R.B., Mariam, Y.H.: In: Sigel, H. (ed.) Metal Ions in Biological Systems, vol. 8, pp. 57–124. Dekker, New York (1979)
Sigel, H., Massoud, S.S., Corfu, N.A.: Comparison of the extent of macrochelate formation in complexes of divalent metal ions with guanosine (GMP2-), inosine (IMP2-), and adenosine 5-monophosphate (AMP2-). The crucial role of N-7 basicity in metal ion–nucleic base recognition. J. Am. Chem. Soc. 116, 2958–2971 (1994)
Noszol, B., Scheller-Krattiger, V., Martin, R.B.: A unified view of carbon bound hydrogen exchange of H(2) in imidazoles and H(8) in purine nucleosides and their metal ion complexes. J. Am. Chem. Soc. 104, 1078–1081 (1982)
Jardetzky, O., Pappas, P., Waide, N.G.: Proton magnetic resonance studies of purine and pyrimidine derivatives. IX. The protonation of pyrimidine in acid solution. J. Am. Chem. Soc. 85, 1657–1658 (1963)
Benoit, R.L., Frechette, M.: 1H and 13C nuclear magnetic resonance and ultraviolet studies of the protonation of cytosine, uracil, thymine, and related compounds. Can. J. Chem. 64, 2348–2352 (1986)
Roberts, B.W., Lambert, J.B., Roberts, J.D.: Nitrogen-15 magnetic resonance spectroscopy. VI. Pyrimidine derivatives. J. Am. Chem. Soc. 87, 5439–5441 (1965)
Kramer-Schnabel, U., Linder, P.W.: Substituent effects in the protonation and complexation with copper(II) ions of organic monophosphate esters. A potentiometric and calorimetric study. Inorg. Chem. 30, 1248–1254 (1991)
Rees, D.C.: Experimental evaluation of the effective dielectric constant of proteins. J. Mol. Biol. 141(3), 323–326 (1980)
Rogersa, N.K., Mooreb, G.R., Sternberga, M.J.E.: Electrostatic interactions in globular proteins: calculation of the pH dependence of the redox potential of cytochrome C551. J. Mol. Biol. 182, 613–616 (1985)
Åkerlöf, G., Short, O.A.: The dielectric constant of dioxane–water mixtures between 0 and 80°-correction. J. Am. Chem. Soc. 75, 6357 (1953)
Doğan, A., Köseoğlu, F., Kılıç, E.: The stability constants of copper(II) complexes with some α-amino acids in dioxane water mixtures. Anal. Biochem. 295, 237–239 (2001)
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
El-Sherif, A.A., Shoukry, M.M., Hosny, W.M. et al. Complex Formation Equilibria of Unusual Seven-Coordinate Fe(EDTA) Complexes with DNA Constituents and Related Bio-relevant Ligands. J Solution Chem 41, 813–827 (2012). https://doi.org/10.1007/s10953-012-9833-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10953-012-9833-4