Potentiometric, spectrophotometric, conductimetric and thermodynamic studies on some transition metal complexes derived from 3-methyl-1-phenyl- and 1, 3-diphenyl-4-arylazo-5-pyrazolones
ABSTRACT
A new 3methyl1phenyl4arylazo5pyrazolone and 1, 3diphenyl4arylazo5pyrazolone have been synthesized and characterized by elemental analysis, IR, mass and 1H NMR spectra. The acid dissociation constants (pKa values) of the investigated ligands were determined potentiometrically and spectrophotometrically. The stability constants of the transition metal ions (VO2+, Cr3+, Mn2+, Co2+, Ni2+, Cu2+ and Zn2+) with the investigated ligands were determined potentiometrically at different ionic strengths (0.167, 0.1, 0.05 and 0.025 M) NaCl at 25oC and different temperature (25, 30, 35, and 45oC). The values of stability constants were found to decrease with increasing ionic strengths and temperature. The stoichiometries were studied using spectrophotometric and conductimetric methods, the results indicate the existence of 1:1 and 1:2 (M:L) metal:ligand species. The relationships between the stability constants of the complexes, ionization constants of the ligands have been discussed and correlated. The thermodynamic parameters (?G, ?H and ?S) and the thermodynamic stability constants for all of the investigated complexes were determined potentiometrically.
A new 3methyl1phenyl4arylazo5pyrazolone and 1, 3diphenyl4arylazo5pyrazolone have been synthesized and characterized by elemental analysis, IR, mass and 1H NMR spectra. The acid dissociation constants (pKa values) of the investigated ligands were determined potentiometrically and spectrophotometrically. The stability constants of the transition metal ions (VO2+, Cr3+, Mn2+, Co2+, Ni2+, Cu2+ and Zn2+) with the investigated ligands were determined potentiometrically at different ionic strengths (0.167, 0.1, 0.05 and 0.025 M) NaCl at 25oC and different temperature (25, 30, 35, and 45oC). The values of stability constants were found to decrease with increasing ionic strengths and temperature. The stoichiometries were studied using spectrophotometric and conductimetric methods, the results indicate the existence of 1:1 and 1:2 (M:L) metal:ligand species. The relationships between the stability constants of the complexes, ionization constants of the ligands have been discussed and correlated. The thermodynamic parameters (?G, ?H and ?S) and the thermodynamic stability constants for all of the investigated complexes were determined potentiometrically.
Cite this paper
AbdelLatif, S. , Mansour, S. and Fatouh, A. (2010) Potentiometric, spectrophotometric, conductimetric and thermodynamic studies on some transition metal complexes derived from 3-methyl-1-phenyl- and 1, 3-diphenyl-4-arylazo-5-pyrazolones. Natural Science, 2, 793-802. doi: 10.4236/ns.2010.28100.
AbdelLatif, S. , Mansour, S. and Fatouh, A. (2010) Potentiometric, spectrophotometric, conductimetric and thermodynamic studies on some transition metal complexes derived from 3-methyl-1-phenyl- and 1, 3-diphenyl-4-arylazo-5-pyrazolones. Natural Science, 2, 793-802. doi: 10.4236/ns.2010.28100.
References
[1] Wisniewski, M.Z. (1997) Pd(II) complexes with some derivatives of pyrazol5one. Polish Journal of Chemistry, 71(2), 259260. [2] Lu, J., Zhang, L., Liu, L., Liu, G., Jia, D., Wu, D. and Xu, G. (2008) Study of fluorescence properties of several 4acyl pyrazolone derivatives and their Zn(II) complexes. Spectrochimica Acta Part A, 71(3), 10361041. [3] Kuncheria, B. and Indrasenan, P. (1988) Thorium (IV) nitrate complexes with some substituted pyrazole5ones. Indian Journal of Chemistry, 27A, 10051007. [4] Vogel, I. (1978) A text book of practical organic chemistry. 4th Edition, Longman, London. [5] Tantawy, F., Goda, F. and Abdelal, A.M. (1995) Synthesis and characterization of certain new 3methyl4(subs tituted phenylazo) isoxazol5ones and 3methyl4 (substituted phenylazo)pyrazole5ones as potential antibacterial agents. The Chinese Pharmaceutical Journal, 47(1), 3745. [6] Rao, S. and Mittra, A.S. (1978) Synthesis and fungitoxicity of 1phenyl3methyl4mono arylidene2pyrazolin 5thione. Journal of the Indian Chemical Society, 55(7), 745746. [7] Fitton, A.O. and Smalley, R.K. (1968) Practical heterocyclic chemistry. Academic Press, London and New York. [8] Karci, F. and Ertan, N. (2002) Hetarylazo disperse dyes derived from 3methyl1(3′, 5′dipiperidinostriazinyl) 5pyrazolone as coupling component. Dyes and Pigments, 55(23), 99108. [9] Ibrahim, S.A., ElGahami, M.A., Khafagi, Z.A. and ElGyar, S.A. (1991) Structure and antimicrobial activity of some new azopyrazolone chelates of Ni(II) and Cu(II) acetates, sulfates and nitrates. Journal of Inorganic Biochemistry, 43(1), 17. [10] AbdelLatif, S.A. (2001) Synthesis and characterization of some 3phenyl4arylazo5pyrazolones with La(III), Ce(III), Th(IV) and UO2(VI) complexes. Synthesis and Reactivity in Inorganic, MetalOrganic and Chemistry, 31(8), 13551374. [11] AbdelLatif, S.A. and Hassib, H.B. (2002) Studies of Mn(II), Co(II), Ni(II) and Cu(II) Chelates with 3 Phenyl4(pmethoxyphenylazo)5pyrazolone. Journal of Thermal Analysis and Calorimetry, 68(3), 983995. [12] Hassib, H.B. and AbdelLatif, S.A. (2003) Potentiometric, spectrometric thermal and conductimetric studies on some 3phenyl4(arylazo)5pyrazolones and their complexes with divalent cobalt metal ion. Spectrochimica Acta Part A, 59(11), 24252434. [13] Sarin, R. and Munshi, K.N. (1972) Thermodynamics of complex formation of indium metal ion with mercapto hydroxyl and amino substituted succinic acid. Journal of Inorganic and Nuclear Chemistry, 34(2), 581590. [14] Britton, H.T.S. (1952) Hydrogen ions. 2nd Edition, Chapman and Hall, London. [15] West, T.S. (1969) Complexemetry with EDTA and related reagents. 3rd Edition, B. D. H. Chemical Ltd Poole, London,. [16] Vogel, I. (1956) Practical organic chemistry including quantitative organic analysis. 3rd Edition, Longmans, London. [17] Irving, H. and Rossotti, H.S. (1953) Methods for computing successive stability constants from experimental formation curves. Journal of Chemical Society, 3397 3405. [18] Zumdal, S.S. (1997) Chemistry. 4th Edition, Houghton Mifflin Company. [19] Vogel, A.I. (1956) Practical organic chemistry including quantitative organic analysis. 3rd Edition, Longmans, London. [20] Issa, Y.M., AbdelGhani, N.T. and AbdelLatif, S.A. (1996) Spectrophotometric studies on some hydroxy nitrocoumarins. Egyptian Journal of Chemistry, 39(3), 235248. [21] Bauer, H.H., Christian, G.D. and O'Reilly, J.E. (1978) Instrumental analysis. Allyn and Bacon Inc. [22] McMurry, J. (2000) Organic chemistry. 5th Edition, Brooks/Cole, USA. [23] Schwarzenbach, G. and Flaschk, H. (1969) Complexometric titrations. Methuen and Co. Ltd., London. [24] Moeller, T., Martin, D.F., Thompson, L.C., Ferrus, R., Feistel, G.R. and Randal, W.J. (1965) The coordination chemistry of yttrium and the rare earth metal ions. Chemical Reviews, 65(1), 150. [25] Gutmann, K. (1966) Conductimetric titration of charge transfer complexes in solution. Electrochimica Acta, 11(6), 555568. [26] Singh, P. and Ojha, A.C. (1980) Synthesis of Nisoni ctinyl3methyl4(substitutedhydrazono)2pyrazolin5 one. Journal of the Indian Chemical Society, 57(12), 11721173. [27] Snavely, F.A. and Krecker, B.D. (1959) Metal derivatives of arylazopyrazolone dyes III, molarity quotients of para and metasubstituted pyrazolone dyes. Journal of the American Chemical Society, 81(16), 41994200. [28] William, W.P. (1993) Inorganic chemistry. 2nd Edition, Academic Press Inc. [29] Manku, G.S., Gupta, R.D., Bhat, A.N. and Jain, B.D. (1968) Determination of the stability constants of some lanthanon complexes with 1nitroso2naphthol, 2ni troso1naphthol, and 3nitroso4hydroxycoumarin. Journal of the Less Common Metals, 16(4), 343350. [30] Debye, P. and Hückel, E. (1923) Physik. Z., 24, 185206. [31] Saxena, R.S. and Gupta, A. (1984) Potentiometric determination of dissociation constants of dithiodipropionic acid in different media. Journal of the Electrochemical Society India, 33(1), 8990. [32] Yadav, S.S. and Saxena, R.S. (2009) Formation constants and thermodynamic parameters of some triligand complexes of lanthanides. Journal of the Indian Chemical Society, 86(2), 168170.
[1] Wisniewski, M.Z. (1997) Pd(II) complexes with some derivatives of pyrazol5one. Polish Journal of Chemistry, 71(2), 259260. [2] Lu, J., Zhang, L., Liu, L., Liu, G., Jia, D., Wu, D. and Xu, G. (2008) Study of fluorescence properties of several 4acyl pyrazolone derivatives and their Zn(II) complexes. Spectrochimica Acta Part A, 71(3), 10361041. [3] Kuncheria, B. and Indrasenan, P. (1988) Thorium (IV) nitrate complexes with some substituted pyrazole5ones. Indian Journal of Chemistry, 27A, 10051007. [4] Vogel, I. (1978) A text book of practical organic chemistry. 4th Edition, Longman, London. [5] Tantawy, F., Goda, F. and Abdelal, A.M. (1995) Synthesis and characterization of certain new 3methyl4(subs tituted phenylazo) isoxazol5ones and 3methyl4 (substituted phenylazo)pyrazole5ones as potential antibacterial agents. The Chinese Pharmaceutical Journal, 47(1), 3745. [6] Rao, S. and Mittra, A.S. (1978) Synthesis and fungitoxicity of 1phenyl3methyl4mono arylidene2pyrazolin 5thione. Journal of the Indian Chemical Society, 55(7), 745746. [7] Fitton, A.O. and Smalley, R.K. (1968) Practical heterocyclic chemistry. Academic Press, London and New York. [8] Karci, F. and Ertan, N. (2002) Hetarylazo disperse dyes derived from 3methyl1(3′, 5′dipiperidinostriazinyl) 5pyrazolone as coupling component. Dyes and Pigments, 55(23), 99108. [9] Ibrahim, S.A., ElGahami, M.A., Khafagi, Z.A. and ElGyar, S.A. (1991) Structure and antimicrobial activity of some new azopyrazolone chelates of Ni(II) and Cu(II) acetates, sulfates and nitrates. Journal of Inorganic Biochemistry, 43(1), 17. [10] AbdelLatif, S.A. (2001) Synthesis and characterization of some 3phenyl4arylazo5pyrazolones with La(III), Ce(III), Th(IV) and UO2(VI) complexes. Synthesis and Reactivity in Inorganic, MetalOrganic and Chemistry, 31(8), 13551374. [11] AbdelLatif, S.A. and Hassib, H.B. (2002) Studies of Mn(II), Co(II), Ni(II) and Cu(II) Chelates with 3 Phenyl4(pmethoxyphenylazo)5pyrazolone. Journal of Thermal Analysis and Calorimetry, 68(3), 983995. [12] Hassib, H.B. and AbdelLatif, S.A. (2003) Potentiometric, spectrometric thermal and conductimetric studies on some 3phenyl4(arylazo)5pyrazolones and their complexes with divalent cobalt metal ion. Spectrochimica Acta Part A, 59(11), 24252434. [13] Sarin, R. and Munshi, K.N. (1972) Thermodynamics of complex formation of indium metal ion with mercapto hydroxyl and amino substituted succinic acid. Journal of Inorganic and Nuclear Chemistry, 34(2), 581590. [14] Britton, H.T.S. (1952) Hydrogen ions. 2nd Edition, Chapman and Hall, London. [15] West, T.S. (1969) Complexemetry with EDTA and related reagents. 3rd Edition, B. D. H. Chemical Ltd Poole, London,. [16] Vogel, I. (1956) Practical organic chemistry including quantitative organic analysis. 3rd Edition, Longmans, London. [17] Irving, H. and Rossotti, H.S. (1953) Methods for computing successive stability constants from experimental formation curves. Journal of Chemical Society, 3397 3405. [18] Zumdal, S.S. (1997) Chemistry. 4th Edition, Houghton Mifflin Company. [19] Vogel, A.I. (1956) Practical organic chemistry including quantitative organic analysis. 3rd Edition, Longmans, London. [20] Issa, Y.M., AbdelGhani, N.T. and AbdelLatif, S.A. (1996) Spectrophotometric studies on some hydroxy nitrocoumarins. Egyptian Journal of Chemistry, 39(3), 235248. [21] Bauer, H.H., Christian, G.D. and O'Reilly, J.E. (1978) Instrumental analysis. Allyn and Bacon Inc. [22] McMurry, J. (2000) Organic chemistry. 5th Edition, Brooks/Cole, USA. [23] Schwarzenbach, G. and Flaschk, H. (1969) Complexometric titrations. Methuen and Co. Ltd., London. [24] Moeller, T., Martin, D.F., Thompson, L.C., Ferrus, R., Feistel, G.R. and Randal, W.J. (1965) The coordination chemistry of yttrium and the rare earth metal ions. Chemical Reviews, 65(1), 150. [25] Gutmann, K. (1966) Conductimetric titration of charge transfer complexes in solution. Electrochimica Acta, 11(6), 555568. [26] Singh, P. and Ojha, A.C. (1980) Synthesis of Nisoni ctinyl3methyl4(substitutedhydrazono)2pyrazolin5 one. Journal of the Indian Chemical Society, 57(12), 11721173. [27] Snavely, F.A. and Krecker, B.D. (1959) Metal derivatives of arylazopyrazolone dyes III, molarity quotients of para and metasubstituted pyrazolone dyes. Journal of the American Chemical Society, 81(16), 41994200. [28] William, W.P. (1993) Inorganic chemistry. 2nd Edition, Academic Press Inc. [29] Manku, G.S., Gupta, R.D., Bhat, A.N. and Jain, B.D. (1968) Determination of the stability constants of some lanthanon complexes with 1nitroso2naphthol, 2ni troso1naphthol, and 3nitroso4hydroxycoumarin. Journal of the Less Common Metals, 16(4), 343350. [30] Debye, P. and Hückel, E. (1923) Physik. Z., 24, 185206. [31] Saxena, R.S. and Gupta, A. (1984) Potentiometric determination of dissociation constants of dithiodipropionic acid in different media. Journal of the Electrochemical Society India, 33(1), 8990. [32] Yadav, S.S. and Saxena, R.S. (2009) Formation constants and thermodynamic parameters of some triligand complexes of lanthanides. Journal of the Indian Chemical Society, 86(2), 168170.