Composition, Stability and Probable Structure of a Colourless Organometallic Complex (Gd(III)-Malic Acid)

DOI: 10.4236/ojpc.2013.31007   PDF   HTML   XML   3,765 Downloads   6,762 Views   Citations

Abstract

The formation of colourless gadolinium complexes (x,y,z), between x gadolinium ions, y ligands and z protons, of some organic acids, has been studied in aqueous solution. In this work we present the results of investigations on the interaction of the gadolinium ion (Gd3+) with malic acid (C4H6O5, a-hydroxyl dicarboxylic acid), in dilute aqueous solution for pH values between 5.5 and 7.5. Colourless gadolinium complexes of malate ions have no absorption band UV-visible, the indirect photometric detection (IPD) technique was used and studies have identified a major tri-nuclear complex of malate ion (OOC-CH2-CHOH-COO). The formation of this new colourless complex is derived from three Gd(III) ions that react with two malate ions and two hydronium ions (H3O+), giving for this colourless complex, a (3,2,2) composition and apparent stability constant depends on the acidity of the medium, with logK'322 = 18.88 ± 0.05 at pH = 6.30. To complement previous results and to propose a probable structure for this new complex detected in solution, studies of IR spectroscopy have been conducted to identify the chelation sites for both ligands. The results were analysed and show that this organometallic gadolinium complex, contains two different sites, respectively, two lateral tetradentate mono-nuclear sites and a single central bidentate mono-nuclear site. From these results, the reaction of formation, the stability constant and the probable structure of this new colourless organometallic gadolinium complex are proposed.

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M. Riri, O. Kamal, A. Benjjar, F. Serdaoui and M. Hlaibi, "Composition, Stability and Probable Structure of a Colourless Organometallic Complex (Gd(III)-Malic Acid)," Open Journal of Physical Chemistry, Vol. 3 No. 1, 2013, pp. 49-58. doi: 10.4236/ojpc.2013.31007.

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1] R. D. Rocklin, “Detection in ion Chromatography,” Journal of Chromatography A, Vol. 546, No. 1-2, 1991, pp. 175-187.
[2] J. F. Verchère and A. M. Dona, “Exchange Methods for the Indirect Photometric Determination of Anions and Organic Molecules,” Analusis, Vol. 20, No. 8, 1992, pp. 437-450.
[3] S. E. Meek and D. J. Pietrzyk, “Liquid Chromatographic Separation of Phosphorus Oxo Acids and Other Anions with Post-Column Indirect Fluorescence Detection by Aluminum-Morin,” Analytical Chemistry, Vol. 60, No. 14, 1988, pp. 1397-1400. doi:10.1021/ac00165a010
[4] P. Morin, C. Fran?ois, M. Dreux, “Séparation de Cations et d’Anions Inorganiques par éléctrophorèse Capillaire Ionique Avec une Détection Spectrométrique UV Indirecte: Capillary Electrophoresis of Inorganic Cations and Anions with Different Carrier Electrolytes and UV Detection ,” Analusis, Vol. 22, No. 4, 1994, pp. 178-187.
[5] A. M. Lisi, “La Photomertie Indirecte Comme Methode Analytique Pour Letude des complexes incolores des Acides Organiques dans les Solutions Diluées,” ParisVI University, Paris, 1993.
[6] M. Hlaibi, “La Photométrie Indirecte et RMN Pour l’Etude de l’Oxalate Urinaire et Pour l’Etude des Complexes Incolore des Ions UO22+ et WO42-,” Hassan II University, Ain Chock, Casablanca, 1995.
[7] A. Ramshing, J. Rusika and E. H. Hasen, “A New Approach to Enzymatic Assay Based on Flow-Injection Spectrophotometry with Acid-Base Indicators,” Analytica Chimica Acta, Vol. 114, 1980, p. 165-181.
[8] M. Hla?bi, S Chapelle, M. Benaissa and J. F. Verchère, “Structures and Stabilities of Tungstate Complexes of .Alpha.-Hydroxy Acids. 183W NMR Study of the Influence of Ligand Substitutionm,” Inorganic Chemistry, Vol. 34, No. 17, 1995, pp. 4434-4440. doi:10.1021/ic00121a022
[9] M. Hla?bi, M. Benaissa, C. Busatto, J. F. Verchère and S. Chapelle, “A 13C and 183W NMR Study of Acid as a Multisite Ligand in Tungstate Complexes,” Carbohydrate Research, Vol. 278, No. 2, 1995, p. 227. doi:10.1016/0008-6215(95)00266-9
[10] A. Nonat, C. Gateau, P. H. Fries and M. Mazzanti, “Lanthanide Complexes of a Picolinate Ligand Derived from 1,4,7-Triazacyclononane with Potential Application in Magnetic Resonance Imaging and Time-Resolved Luminescence Imaging,” Chemistry, A European Journal, Vol. 12, No. 27, 2006, pp. 7133-7150. doi:10.1002/chem.200501390
[11] N. Chatterton, C. Gateau, M. Mazzanti, J. Pécaut, A. Borel and A. Merbach, “The Effect of Pyridinecarboxylate Chelating Groups on the Stability and electronic Relaxation of Gadolinium Complexes,” Journal of the Chemical Society, Dalton Transactions, Vol. 21, No. 6, 2005, pp. 1129-1135.
[12] I. Kostova, G. Momekov and P. Stancheva, “New Samarium(III), Gadolinium(III), and Dysprosium(III) Complexes of Coumarin-3-Carboxylic Acid as Antiproliferative AgentsMetal-Based Drugs,” Vol. 2007, 2007, 8 pages. doi:10.1155/2007/15925
[13] F. J. Langmyhr and K. S. Klausen, “Complex Formation of Iron (III) with Chrome Azurol S,” Analytica Chimica Acta, Vol. 29, 1963, pp. 149-167. doi:10.1016/S0003-2670(00)88596-7
[14] A. M. Dona and J. F. Verchère, “Analytical Applications of Oxocarbons. Part 3. Specific Spectrophotometric Determination of Oxalic Acid by Dissociation of the Zirconium(IV)-Chloranilate Complex,” Analyst, Vol. 116, 1991, pp. 533-536. doi:10.1039/an9911600533
[15] M. Malt, “Dissoziationskonstanten von Chromazurol S,” Analytica Chimica Acta, Vol. 25, No. 1, 1961, pp. 289-291.
[16] W. Hummel, U. Berner, E. Curti, F. J. Pearson and T. Thoenen, “Nagra/PSI Chemical Thermodynamic Data Base 01/01,” Radiochimica Acta, Vol. 90, No. 9-11, 2002, pp. 805-813. doi:10.1524/ract.2002.90.9-11_2002.805
[17] J. D. Robert and M. C. Caserio, “Problème de Chimie Organique Moderne, ” InterEditions, Paris, 1979, p. 32.
[18] Colthup, Daly, Wiberley, Introduction to Infrared and Raman Spectroscopy, Academic Press, New York, 1990.
[19] N. P. G. Roeges, “A Guide to the Complete Interpretation of Infrared Spectra of Organic Structures,” Wiley, New York, 1994.
[20] N. Sundaraganesan, B. D. Joshua, M. Rajamoorthy and C. H. Gangadhar, “FT-IR, FT-Raman Spectra and Ab-Initio DFT Vibrational Analysis of 2-Chloro-5-Aminopyridine,” Indian Journal of Pure & Applied Physics, Vol. 45, No. 12, 2007, pp. 969-978
[21] Horiba Jobin Yvon Inc., 3880 Park Avenue, Edison, NJ 08820-3012. USA
[22] E. Smith and G. Dent, “Modern Raman Spectroscopy—A Practical Approach,” Wiley, 2005, pp. 15-19.
[23] N. Sundaraganesana, S. Ilakiamania, H. Saleema, Piotr. M. Wojciechowskib and D. Michalsk, “FT-Raman and FT-IR Spectra, Vibrational Assignments and Density Functional Studies of 5-Bromo-2-Nitropyridine,” Spectrochimica Acta, Part A, Vol. 61, No. 13-14, 2005, pp. 2995-3001.
[24] L. Padmaja, T. Vijayakumar, I. H. Joe, C. P. R. Nair, V. S. Jayakumar, “Vibrational Spectral Studies and the Non-Linear Optical Properties of a Novel NLO Material L-Prolinium Tartrate,” Journal of Raman Spectroscopy, Vol. 37, No. 12, 2006, pp. 1427-1441. doi:10.1002/jrs.1575
[25] S. Gunasekaran and S. Ponnusaymy, “Vibrational Spectra and Normal Coordinate Analysis on an Organic Non-Linear Optical Crystal-3-methoxy-4-hydroxy Benzaldehyde,” Indian Journal of Pure & Applied Physics, Vol. 43, No. 11, 2005, pp. 838-843.
[26] K. Malek, E. Podstawka, J. Milecki, G. Schroeder and L. M. Proniewicz, “Structural Features of the Adenosine Conjugate in Means of Vibrational Spectroscopy and DFT,” Biophysical Chemistry, Vol. 142, No. 1-3, 2009, pp. 17-26. doi:10.1016/j.bpc.2009.02.007
[27] S. Chapelle, J. P. Sauvage, P. K?ll, J. F. Verchère, “183W NMR Studies of Tungstate Complexes of Carbohydrates. 3. Species Formed with All-threo Alditols Acting as Tridentate, Tetradentate, or Pentadentate Ligands,” Inorganic Chemistry, Vol. 34, No. 4, 1995, pp. 918-923. doi:10.1021/ic00108a024
[28] M. Hla?bi, M. Hor, M. Riri, A. Benjjar and J. F. Verchère, “Multinuclear 183W and 13C NMR and Indirect Photometry Study for the Identification and the Characterization of New Complexes of Sugar Acids,” Journal of Molecular Structure, Vol. 920, No. 1-3, 2009, pp. 310-322. doi:10.1016/j.molstruc.2008.11.016

  
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