Abstract
The formation of mixed ligand complexes of Cu(II) with 2,2′-bipyridyl (Bipy) in the presence of some selected aromatic diamines (L) (L = 3,4-diamino benzoic acid (DABA), 2-hydazinopyridine (hzpy) or 4-chloro-o-phenylenediamine has been studied by pH-metric titrations. Potentiometric measurements show that ternary complexes are formed in a simultaneous manner. The pH-titrations of the reaction mixtures are shown to yield 1:1:1 ternary complex formation. The equilibrium and formation constants of the resulting ternary complexes have been calculated at I = 0.1 mol·dm−3 of NaNO3. The order of stability in terms of the secondary ligands has been found to be DABA > hzpy > CAPA. The stability of ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameters Δlog10 K, Δlog10 β and log10 X. The concentration distributions of various species formed in solution were also evaluated as a function of pH. In addition, the effect of temperature on both the ionization process of the ligands and complex formations for Cu–Bipy–L ternary systems was studied. The thermodynamic parameters were calculated from the temperature dependence of the equilibrium constants and are discussed. The structure of the Cu(II) complexes have been geometrically optimized using the parameterized PM3 semiempirical method.
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Abbreviations
- Bipy:
-
2,2′-Bipyridyl
- CPDA:
-
4-Chloro-o-phenylenediamine
- hzpy:
-
2-Hydrazinopyridine
- DABA:
-
3,4-Diaminobenzoic acid
References
Scoullos, M., Pavlidou, A.: Speciation studies of trace metals in the Gulf of Elefsis, Greece. Croat. Chem. Acta 70, 289–303 (1997)
El-Sherif, A.A., Eldebss, T.M.A.: Synthesis, spectral characterization, solution equilibria, in vitro antibacterial and cytotoxic activities of Cu(II), Ni(II), Mn(II), Co(II) and Zn(II) complexes with Schiff base derived from 5-bromosalicylaldehyde and 2-aminomethylthiophene. Spectrochim. Acta 79A, 1803–1814 (2011)
Teigen, S., Anderson, R., Program on Marine Pollution (PMF): Trace Metals in the Marine Environment, State of the Art and Research Needs. Croatian Society of Chemical Engineers, Zagreb (1992)
Mildvan, A.S., Cohn, M.: Kinetic and magnetic resonance studies of the pyruvate kinase reaction: II. Complexes of enzyme, metal, and substrates. J. Biol. Chem. 241, 1178–1193 (1966)
Bouwman, E., Driessen, W.L., Reedijk, J.: Model systems for type I copper proteins: structures of copper coordination compounds with thioether and azole-containing ligands. Coord. Chem. Rev. 104, 143–172 (1990)
Kaim, W., Schwederski, B.: Bioinorganic Chemistry: Inorganic Elements in the Chemistry of Life. Wiley, New York (1996)
Everson, G.J., Tsai, H.-C.C., Wang, T.-I.: Copper deficiency in the guinea pig. J. Nutr. 93, 533–540 (1967)
Melník, M., Potočnăk, I., ková, L.M., Miklos, D., Holloway, C.E.: Spectral study of copper(II) flufenamates: crystal and molecular structure of bis(flufenamato)di(N, N-diethylnicotinamide) di(aqua) copper(II). Polyhedron 15, 2159–2164 (1996)
El-Sherif, A.A., Shoukry, M.M., Abd-Elgawad, M.A.: Protonation equilibria of some selected α-amino acids in DMSO–water mixture and their Cu(II)-complexes. J. Solution Chem. 42, 412–427 (2013)
Sigel, H., Martin, R.B.: Coordinating properties of the amide bond. Stability and structure of metal ion complexes of peptides and related ligands. Chem. Rev. 82, 385–426 (1982)
Soliman, A.A., Amin, M.A., El-Sherif, A.A., Ozdemir, S., Varlikli, C., Zafer, C.: Synthesis and characterization of novel series of Fe(II)-mixed ligand complexes involving 2,2′-bipyridyl ligand. Dyes Pigments 99, 1056–1064 (2013)
Freinbichler, W., Soliman, A.A., Jameson, R.F., Jameson, G.N.L., Linert, W.: Kinetic study of the complex reaction between copper(II) and 2-(2-hydroxy-3-methoxyphenyl) benzothiazole. Spectrochim. Acta 74A, 30–35 (2009)
El-Sherif, A.A.: Mixed-ligand complexes of 2-(aminomethyl)benzimidazole palladium(II) with various biologically relevant ligands. J. Solution Chem. 35, 1287–1301 (2006)
El-Sherif, A.A.: Mixed ligand complexes of Cu(II)-2-(2-pyridyl)-benzimidazole and aliphatic or aromatic dicarboxylic acids: synthesis, characterization and biological activity. J. Spectrochim. Acta 68(3), 877–882 (2007)
El-Dissouky, A., Shuaib, N.M., Al-awadi, N.M., Abbas, A.B., El-Sherif, A.A.: Synthesis, characterization, potentiometric and thermodynamic studies of transition metal complexes with 1-benzotriazol-1-yl-1-[(p-methoxyphenyl) hydrazono]propan-2-one. J. Coord. Chem. 61, 579–594 (2008)
Jeragh, B., Al-Wahaib, D., El-Sherif, A.A., El-Dissouky, A.: Potentiometric and thermodynamic studies of dissociation and metal complexation of 4-(3-hydroxypyridin-2-ylimino)-4-phenylbutan-2-one. J. Chem. Eng. Data 52, 1609–1614 (2007)
Al-Kandary, J.A., Mandani, F.M.A., Al-Jimaz, A.S., El-Sherif, A.A., Shoukry, M.M.: Synthesis and thermodynamic investigation of 4-amino-6-hydroxy-2-mercapto pyrimidine (AHMP) complexes with some selected divalent metal(II) ions. J. Solution Chem. 36, 247–257 (2007)
Welcher, F.J.: The Analytical Uses of Ethylenediamine Tetraacetic Acid. Princeton, Van Nostand (1965)
HyperChem version 7.5. Hypercube, Inc. (2003)
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)
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, personal communication
Nakamoto, K.: Infrared and Raman Spectra of Inorganic and Coordination Compounds, 4th edn. Wiley, New York (1986)
Soliman, A.A., Mohamed, G.G.: Structural and thermal study of the ternary complexes of copper with salycilidene-2-aminothiophenol and some aminoacids. Thermochim. Acta 421, 151–159 (2004)
Housecroft, C.E., Sharpe, A.G.: Inorganic Chemistry, 2nd edn. Pearson, England (2005)
Lever, A.B.P.: Inorganic Electronic Spectroscopy. Elsevier, Amsterdam (1984)
Chandra, S., Gupta, L.K.: EPR and electronic spectral studies on Co(II), Ni(II) and Cu(II) complexes with a new tetradentate [N4] macrocyclic ligand and their biological activity. Spectrochim. Acta 60A, 1563–1571 (2004)
Kohout, J., Hvastijova, M., Diaz, J.G., Valko, M., Jager, L., Svoboda, I.: Cyanamidonitrate–copper(II) complexes of imidazole ligands: X-ray crystallography and physical investigation. Inorg. Chim. Acta 287, 186–192 (1999)
Geary, W.J.: The use of conductivity measurements in organic solvents for the characterisation of coordination compounds. Coord. Chem. Rev. 7, 81–122 (1971)
Thompson, L.K., Lee, F.L., Gabe, E.J.: Variable antiferromagnetic exchange in a series of binuclear copper(II) complexes of tetradentate (N4) and hexadentate (N6) diazine ligands. Magnetism versus structure, bridging and terminal ligand groups, and chelate ring size. Crystal and molecular structure of 1,4-bis((6-methylpyrid-2-yl)amino)phthalazine](-hydroxo)(nitrato-O)-bis(nitrato)dicopper(II)·0.5H2O. Inorg. Chem. 27, 39–46 (1988)
Pearson, R.G.: Absolute electronegativity and hardness: applications to organic chemistry. J. Org. Chem. 54, 1423–1430 (1989)
Geerlings, P., De Proft, F., Langenaeker, W.: Conceptual density functional theory. Chem. Rev. 103, 1793–1812 (2003)
Speier, G., Csihony, J., Whalen, A.M., Pie-pont, C.G.: Studies on aerobic reactions of ammonia/3,5-di-tert-butylcatechol Schiff-base condensation products with copper, copper(I), and copper(II). Strong copper(II) radical ferromagnetic exchange and observations on a unique N-N coupling reaction. Inorg. Chem. 35, 3519–3524 (1996)
Sagdinc, S., Koksoy, B., Kandemirli, F., Bayari, S.H.: Theoretical and spectroscopic studies of 5-fluoro-isatin-3-(N-benzylthiosemicarbazone) and its zinc(II) complex. J. Mol. Struct. 917, 63–70 (2009)
Xia, S.W., Xu, X., Sun, Y.L., Fan, Y.L., Fan, Y.H., Bi, C.F., Zhang, D.M., Yang, L.R.: Density functional theory study on La complex with Schiff-base as building block. Chin. J. Struct. Chem. 25, 197–203 (2006)
Blower, P.J., Dilworth, J.R., Maurer, R.I., Mullen, G.D., Reynolds, C.A., Zheng, Y.: Towards new transition metal-based hypoxic selective agents for therapy and imaging. J. Inorg. Biochem. 85, 15–22 (2001)
Martell, A.E., Smith, M., Motekaitis, R.J.: NIST Critical Stability Constants of Metal Complexes Database. U.S. Department of Commerce, Gaithersburg (1993)
Powell, K.J., Pettit, L.D.: IUPAC Stability Constants Database. Academic Software, Otley (1997)
Fazary, A.E., Ju, Y.-H.: Nonaqueous solution studies on the protonation equilibria of some phenolic acids. J. Solution Chem. 37, 1305–1319 (2008)
El-Sherif, A.A., Shoukry, M.M., Abd-Elgawad, M.M.A.: Synthesis, characterization, biological activity and equilibrium studies of metal(II) ion complexes with tridentate hydrazone ligand derived from hydralazine. Spectrochim. Acta 98, 307–321 (2012)
Frank, H., Evans, M.W.: Free volume and entropy in condensed systems. III. Entropy in binary liquid mixtures; partial molal entropy in dilute solutions; structure and thermodynamics in aqueous electrolytes. J. Phys. Chem. 13, 507–532 (1945)
Beck, M.T., Nagybal, I.: Chemistry of Complex Equilibria. Wiley, New York (1990)
El-Sherif, A.A.: Synthesis, solution equilibria and antibacterial activity of co(II) with 2-(aminomethyl)-benzimidazole and dicarboxylic acids. J. Solution Chem. 39, 1562–1681 (2010)
Offiong, O.E.: Formation constants and thermodynamic parameters of α-pyridoin thiosemicarbazones with divalent metal ions. Trans. Met. Chem. 23, 553–556 (1998)
Aljahdali, M., Mohamed, S.E., El-Sherif, A.A., Shoukry, M.M., Hosny, W.M., Abd-Almoghny, M.G.: Complex formation equilibria of unusual seven coordinate Fe(III) complexes with DNA constituents. J. Solution Chem. 42, 1663–1679 (2013)
Sigel, H.: Coordination Chemistry. Pergamon Press, Oxford (1980)
Griesser, R., Sigel, H.: Ternary complexes in solution. VIII. Complex formation between the copper(II)–2,2′-bipyridyl 1:1 complex and ligands containing oxygen and/or nitrogen donor atoms. Inorg. Chem. 9, 1238–1243 (1970)
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)
Martin, R.B., Prados, R.: Some factors influencing mixed complex formation. J. Inorg. Nucl. Chem. 36, 1665–1670 (1974)
Aljahdali, M., El-Sherif, A.A.: Equilibrium studies of binary and mixed-ligand complexes of zinc(II) involving 2-(aminomethyl)-benzimidazole and some bio-relevant ligands. J. Solution Chem. 41, 1759–1776 (2012)
Bonomo, R.P., Musumeci, S., Rizzarelii, E., Sammartano, S.: Complexes of Cu(II) with 2,2′-dipyridyl and some cycloalkane-1,1-dicarboxylic acids. Inorg. Chim. Acta 14, 251–257 (1975)
Aljahdali, M., Mohamed, S.E., El-Sherif, A.A., Shoukry, M.M.: Potentiometric and thermodynamic studies of binary and ternary transition metal(II) complexes of imidazole-4-acetic acid and some bio-relevant ligands. J. Solution Chem. 42, 1028–1050 (2013)
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Soliman, A.A., El-Sherif, A.A. & Amin, M.A. Thermodynamics, Chemical Speciation and Complex Formation Equilibria Studies of Binary and Mixed Ligand Complexes of Cu(II) with 2,2′-Bipyridyl and Some Aromatic Diamines. J Solution Chem 44, 77–99 (2015). https://doi.org/10.1007/s10953-015-0293-5
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DOI: https://doi.org/10.1007/s10953-015-0293-5