Journal of Environmental Science International (한국환경과학회지)

The Korean Environmental Sciences Society (한국환경과학회)
권호 표지
DOI QR코드

DOI QR Code

Synthesis of Pentadentate Nitrogen-Oxygen(N3-O2) Ligands with Substituents and the Determination of Stability Constants of Their Heavy(II) Metal Complexes

치환기를 가진 질소-산소(N3-O2)계 리간드 합성과 중금속(II)이온 착물의 안정도상수 결정

  • Kim, Sun-Deuk (Department of Chemistry and Applied Chemistry, Daegu University) ;
  • Seol, Jong-Min (Department of Chemistry and Applied Chemistry, Daegu University)
  • 김선덕 (대구대학교 자연과학대학 화학.응용화학과) ;
  • 설종민 (대구대학교 자연과학대학 화학.응용화학과)
  • Received : 2011.02.09
  • Accepted : 2011.04.20
  • Published : 2011.06.30
Download PDF
⟨ Previous Next ⟩

Abstract

A new $N_3-O_2$ pentadentate ligand, H-BHPT, was synthesized. Hydrochloric acid salts of Br-BHPT, Cl-BHPT, $CH_3O$-BHPT and $CH_3$-BHPT, having Br-, Cl-, $CH_{3-}$ and $CH_3O-$ substituents at the para position of the phenol hydroxyl group of H-BHPT were synthesized. Hydrochloric acid salts of 3OH-BHPT and 4OH-BHPT, having different position of the phenol hydroxyl group of H-BHPT were also synthesized. The synthesis of each ligand was confirmed by C. H. N. atomic analysis and $^1H$ NMR, $^{13}C$ NMR, UV-visible, and mass spectra. The calculated proton dissociation constants ($log{K_n}^H$) of the phenol hydroxyl group and secondary amine group of the synthesized $N_3-O_2$ ligands showed five steps of the proton dissociations. The order of the overall proton dissociation constants ($log{\beta}_p$) of the ligands was Br-BHPT < Cl-BHPT < H-BHPT < $CH_3O$-BHPT < $CH_3$-BHPT. The order agreed with that of Hammett substituent constants (${\delta}_p$). However, dissociation steps of 3OH-BHPT were four and that of 4OH-BHPT was three. The calculated stability constants ($logK_{ML}$) between the ligands and transition metal ions agreed with the order of $log{\beta}_p$ values of the ligands. The order of the stability constants between the transition metal ions with the synthesized ligands was Co(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II). The order agreed well with that of the Iriving-Williams.

Keywords

References

  1. Belaid, S., Djebbar, S., Benali-Baitich, O., Khan, M., Bouet, G., 2007, Complex Formation between Manganese, Nickel, Copper and a Series of New Ligands Derived from N,N'-O-phenylenebis (salicylideneimine), C. R. Chime, 10, 568-572. https://doi.org/10.1016/j.crci.2006.09.012
  2. Chang, B. D., Park, C. I., Kye, Y. H., Lee, I. M., 2004, Treatment of Wastewater from Plating of Copper Element Using Organic Solvent Eluent in Chelating Resin, J. Korea Society of Waste Management, 21(10), 913-916.
  3. Chen, J. H., Kao, Y. Y., Lin, C. H., Yang, F. R., 2005, Surface modification of Amberlite XAD-4 resin with D(2)EHPA by a two-step, solvent-nonsolvent procedure and the application on the separation of lead and copper ions, Separation Science and Technology, 39(9), 2067-2090. https://doi.org/10.1081/SS-120035938
  4. Cabbiness, D. K., Margerum, D. W., 1969, Macrocyclic Effect on the Stability of Copper(II) Tetramine Complexes, J. Am. Chem. Soc., 91(23), 6540-6541. https://doi.org/10.1021/ja01051a091
  5. Choi, K. S., 1988, Removal of Heavy Metal Ions form Wastewater by Ion Exchange, J. of Kor. Soc. Env. Engs., 10(1), 1-15.
  6. Choi, K. S., Lee, I. H., Kim, Y. N., 1991, A Study on Complex Formation of Heavy Metal Ions with N,N'-Oxalybis(salicylaldehyde hydrazone), J. Korean Chemical Society, 35(2), 135-139.
  7. Coleman, W. M., Taylor, L. T., 1978, Reversible $\mu$-Peroxo Complexes of Manganese(II), Inorganica Chimica Acta, 30, 291-293. https://doi.org/10.1016/S0020-1693(00)88982-3
  8. Coleman, W. M., Taylor, L. T., 1980, Reactivity of Dioxygen and Nitrogen Oxide with Manganese Complexes Containing Hexadentate Ligands, 42, 683-687.
  9. Coleman, W. M., Taylor, L. T., 1977, Oxygenation Studies of Manganese (II)Complexes Containing Linear Pentadentate Ligands, Inorganic Chemistry, 16(5), 1114-1119. https://doi.org/10.1021/ic50171a028
  10. Coleman, W. M., 1981, Relationships between Ligand Carbon-13 Chemical Shifts and Reduction Potentials of Mn(III) Complex, Inorg. Chim. Acta., 53, 191-193. https://doi.org/10.1016/S0020-1693(00)84792-1
  11. Duer, M. J., Gerloch, M., 1989, Ligand Fields from Misdirected Valency.5. Consequences for Spectral Intensity Distributions, Inorganic Chemistry, 28(23), 4260-4264. https://doi.org/10.1021/ic00322a016
  12. Furtsch, T. A., Taylor, L. T., 1982, An X-ray Photoelectron Spectroscopy Study of a Series of Manganese Complexes Containing Schiff Base Ligands, Inorganica Chimica Acta, 61, 211-215. https://doi.org/10.1016/S0020-1693(00)89142-2
  13. Goswami, A., Singh, A. K., 2002, 1,8-Dihydroxyanthraquinone anchored on silica gel: synthesis and application as solid phase extractant for lead(II), zinc(II) and cadmium(II) prio to their determination by flame atomic absorption spectrometry, Talanta, 58, 669-678. https://doi.org/10.1016/S0039-9140(02)00374-0
  14. Gehm, H. W., Bregman, J. I., 1976, Water Resources and pollution Control, Van Nostrand Reinhold Company, New York, 84-131.
  15. Jerry, M., 1968, Advanced Organic Chemistry: Reaction, Mechanisms and Structure, McGraw Hill Book Company, New York, 238-245.
  16. Kara, D. M., Alkan, M., 2001, Selective preconcentration, separation and speciation of ferric iron in different samples using N,N'-bis(2-hydroxy- 5-bromobenzyl) 1,2-diaminopropane, Talanta, 55, 415-423. https://doi.org/10.1016/S0039-9140(01)00443-X
  17. Kim, Y. S., In, G., Kim, M. H., Choi, J. M., 2006, Fundamental Study on Solvent Sublation Using Salphen and Its Application for Separative Determination of Trace Ni(II),Co(II) and Cu(II) in Water Samples" Bull. Korean Chem. Soc., 27(11), 1757-1762. https://doi.org/10.5012/bkcs.2006.27.11.1757
  18. Kim, Y. S., In, G., Choi, J. M., 2006, Solid Phase Extraction of Trace Cu (II), Mn(II), Pb(II) and Zn (II) in Water Samples with Pulverized Silikasalen$( NEt_2)_2$ , Bull. Korean Chem. Soc., 27(10), 1557-1561. https://doi.org/10.5012/bkcs.2006.27.10.1557
  19. Kim, Y. S., In, G., Han C. W., Choi, J. M., 2005, Studies on synthesis and application of XAD-4- salen resin for separation and determination of trace elements by solid phase extraction", Microchemical Journal 80, 151-157. https://doi.org/10.1016/j.microc.2004.07.020
  20. Kilic, E., Koseoglu, F., Basgut, O., 1994, Protonation constants of some pyridine derivatives in ethanolwater mixtures, Anal. Chim. Acta, 294, 215-220. https://doi.org/10.1016/0003-2670(94)80197-5
  21. Kim, S. D., Lee, H. W., Seol, J. M., 2010, Synthesis of New Nitrogen-Oxygen($N_3-O_2$) Pentadentate Ligands and the Substituent Effect on the Stability Constants of the Heavy(II) Metal Complexes, J. of the Environmental Science, 19(7), 849-860. https://doi.org/10.5322/JES.2010.19.7.849
  22. Kim, S. D., Song, C. I., Kim, J. K., Kim, J. S., 2004, Synthesis of Schff-Base Ligands and Determination of Stability Constants of Their Transition Metal(II) Complexes, J. of the Environmental Science, 13(9), 835-843. https://doi.org/10.5322/JES.2004.13.9.835
  23. Kolis, J. W., Hamilton, D. E., Kildahl, N. K., 1979, Nickel(II) and Copper(II) Complexes Linear Pentadentate Ligands Derived from Substituted o-Hydroxyaceto- and o-Hydroxybenzophenones, Inorganic Chemistry, 18(7), 1826-1660. https://doi.org/10.1021/ic50197a022
  24. Kohli, R. K., Gopalakrishnan, K., Bhattacharya, P. K., 1980, Study of $\pi$ Interaction in Metal-Schff Base Complexes, J. inorg. nucl. Chem., 43,331-333.
  25. Koseoglu, F., Kilic, E., Canel, E., Yilmaz, N., 1994, Protonation constants of some substituted salicylideneanilines in ethanol-water mixtures, Anal. Chim. Acta, 293, 87-94. https://doi.org/10.1016/0003-2670(94)00077-8
  26. Koseoglu, F., Kilic, E., Uysal, D., 1995, Protonation constants of some substituted 2-hydroxy-1-naphthalideneanilines in dioxan-water mixtures, Talanta., 42, 1875-1882. https://doi.org/10.1016/0039-9140(95)01649-X
  27. Lee, J. S., Choi, B. S., 2008, A Study on the Separation and Determination of The Rare Earth Elements by the AG${\circledR}$50W-X8 Cation Exchange Resin, Analytical Science ＆ Technology, 21(4), 272-278.
  28. Lee, J. J., Yu, Y. H., Cho, B. R., 1988, Removal of Heavy Metal Chelates by Granular Activated Carbon, J. Kor. Soc. Env. Eng., 10(2), 25-30.
  29. Lin, H. K., Wang, X., Su, X., Zhu, S. R., Chen, Y. T., 2002, Synthesis and Thermodynamic properties of Novel Tripod Ligands and Their Cobalt(II), Nikel (II), Copper(II) and Zinc(II)Complex, Trans. Metal. Chem., 27, 384-389. https://doi.org/10.1023/A:1015051002413
  30. Martell, A. E., Motekaitis, R. J., 1992, Determination and Use of Stability Constants. 2nd Ed. VCH, N. Y, 7-24.
  31. Masahiko, M., Takeo, T., 1999, Novel sorbent extraction technique using a chelating agent impregnated porous PTFE filter tube: preconcentration of In(III) with a bis(2-ethylhexyl) hydrogen phosphate (HDEHP) loaded porous PTFE filter tube, Anal. Commun., 36, 185-188. https://doi.org/10.1039/a902146i
  32. Motekaitis, R. J., Martell, A. E., 1992, Stabilities of Metal Complexes of the Meso and SS Isomers of Oxydisuccinic Acid. Inorganic Chemistry, 31, 11-15. https://doi.org/10.1021/ic00027a004
  33. Parsons, G. H., Rochester, C. H., 1975, Acid Ionization Constants of 4-Substitutes Phenols in Methanol+ Water Mixtures. J. Chem. Soc. Faraday, 71, 1058- 1068. https://doi.org/10.1039/f29757101058
  34. Tchobanoglous, G., 1988, Waste Engineering 2nd., McGraw-Hill, 201-215.

Cited by

  1. )) Ligands with Substituents and the Determination of Stability Constants of Their Heavy(II) Metal Complexes vol.21, pp.4, 2012, https://doi.org/10.5322/JES.2012.21.4.421