Synthesis of New N,N,O Tridentate Ligands and Determination of Stability Constants of Transition Metal Complexes by Potentiometry

새로운 N,N,O계 세 자리 리간드의 합성과 전위차적정법에 의한 전이금속 착물의 안정도상수의 결정

  • Kim, Sun-Deuk (Department of Chemistry and Applied Chemistry, Daegu University) ;
  • Lee, Do-Hyub (Department of Chemistry and Applied Chemistry, Daegu University)
  • 김선덕 (대구대학교 화학.응용화학과) ;
  • 이도협 (대구대학교 화학.응용화학과)
  • Published : 2006.08.01


Hydrobromic acid salts of new N, N, O tridentate ligands containing phenol, 2-[(2-Methylamino- ethyl- amino)-methyl]-phenol(H-MMP. 2HBr), 5-Bromo-2-[(2-Methylamino-ethylamino)-methyl]-phenol (Br- MMP. 2HBr), 5-Chloro-2-[(2-Methylamino-ethylamino)-methyl]-phenol(Cl-MMP. 2HBr), 5-Methyl-2-[(2-Methylamino-ethylamino)-methyl]-phenol(Me-MMP. 2HBr), 5-Methoxy-2-I(2-Methylamino-ethylamino)- methyl]-phenol(MeO- MMP. 2HBr) and. 1-[(2-Methylamino-ethylamino)- methyl]-naphthalen-2-ol(Nap- MMP. 2HBr) were synthesized. The synthesized ligands were confirmed by C. H. N. atomic analysis, UV-visible and IR spectroscopies, $^1$H NMR, $^{13}$C NMR and mass analysis. The potentiometry study revealed that the proton dissociation constants(logK$_n^H$) of the synthesized ligands and stability constants (logK$_{ML}$, logK$_{LM2}$) of transition metal complexes of Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II) ions occurred in three steps and the order of the calculated overall proton dissociation constants(log$\beta_p$) and stability constants (logK$_{ML}$) of ligands was Br-MMP. 2HBr < Cl-MMP 2HBr < H-MMP. 2HBr < Nap-MMP. 2HBr < Me-MMP. 2HBr < MeO-MMP. 2HBr. The order showed a similar trend to that of Hammett substituent constants($\delta_p$). The synthesized ligands usually form 2:1(ML$_2$) complexes with transition metal ions. The order of the stability constants of each transition metal ions was Co(II) < Ni(II) < Cu(II) ;> Zn(II) ;> Cd(II) ;> Pb(II).


  1. 김광수, 1988, 공업용수 처리의 이론과 실제, 기적연구사, 5pp
  2. Choi, K. S., 1988, Removal of Heavy Metal Ions form Wastewater by Ion Exchange, J. of Kor. Soc. of Env. Engs, 10(2), 25-30
  3. Adamski, W., 1984, Adsorption in Wastewater Treatment, Effluent and Water Treatment Journal, 34(12), 225-229
  4. Lee, J. J., Y. H. Yu and B. R. Cho, 1988, Removal of Heavy Metal Chelates by Granular Activated Carbon, J. of Kor. Soc. of Env. Engs, 10(1), 1-15
  5. Tchobanoglous, G., 1988, Waste Engineering, 2nd., McGraw-Hill, 201pp
  6. Noyes, R., 1994, Unit Operation in Environmental Engineering, Noyes, 121pp
  7. Choi, K S., I. H. Lee and Y. N. Kim, 1991, A Study on Complex Formation of Heavy Metal Ions with N,N' -Oxalybistsalicylaldehyde hydrazone), J. of the Kor. Chern. Soc. 35(2), pp.135-139
  8. Suzuki, M., 1994, Adsorption Engineering, Elsevier, 125pp
  9. Basgut, O., Z. Durmus, O. Atakol and E. Kilic, 2002, Liquid-membrane electrode sensitive to ammonia and aliphatic amines based on 1-[(2-oxyphenyl)iminomethyl]-2-oxybenzene-O,O' ,N-arnmin-nickel(ll) complex, Talanta, 57, 813-817
  10. Costes, J. P. and M. I. Fernandez-Garcia, 1995, Easy synthesis of 'half-units': their use as ligands or as precursors of non-symmetrical Schiff base complexes, Inorg. Chim. Acta, 237, 57-63
  11. Tandon, S. S., S. Chander and L. K Thompson, 2000, Ligating properties of tridentate Schiff base, 2-[[(2-pyridinylmethyl) iminolmethyllphenol (HSALIMP) and 2-[[[2-(2 -pyridinyl)DethyI]-imino]methyl]phenol(HSALIEP) with zinc(II), cadrnium(ll), nickel(II) and manganese(lll) ions, X-ray crystal structures of the [Zn(SALIEP](NO_{3})]_{2} dimer [Mn(SALIEP)_{2}](ClO_{4}) and [Zn(AMP)_{2}(NO_{3})_{2}], Inorg, Chirn. Acta., 300(302), 683-692
  12. Choi, Y. K, M. S. Song, C. P. Rim and K. H. Chjo, 1995, Synthesis of tridentate schiff base molybdenum(v) complexes and their electrochemical properties in aprotic solvents, J. Kor. Chem. Soc., 39(1), 47-56
  13. Sacconi, L., M. Ciampolini and G. P. Speroni, 1965, High-spin hexa-, penta-, and tetracoordinated complexes of cobalt(ll) with schiff base formed from salicylaldehydes and N,N-substituted ethylenediamines, Inorg, Chem, 4(8), 1116-1119
  14. Asada, H., M. Ozeki, M. Fujiwara and T. Matsushita, 2002, Structure of four types of novel high-valent manganese complexes obtained by the reaction of $KMnO_{4}$ with tridentate schiff base ligands, Polyhedron, 21, 1139-1148
  15. Lin, H. K., X. Wang, X. C. Su, S. R. Zhu and Y. T. Chen, 2002, Synthesis and thermodynamic properties of novel tripod ligands and their cobalt(ll), nikel(ll), copper(ll) and Zinc(ll) complexes, Trans. Metal Chemistry, 27, 384-389
  16. Kim, S. D., J. K. Kim and W. S. lung, 1998, Protonation and stability constants for $CO^{2+}$, $Ni^{2+}$, $Cu^{2+}$ and $Zn^{2+}$ of two open-chain hexadentate N6 ligands containing two pyridyl groups: crystal structures of their Ni(II) complexes, Polyhedron, 17, 1223-1229
  17. Xie, Y. S., X. T. Liu, M. Zhang, K. J. Wei and Q. L. Liu, 2005, Supramolecular structures of Co(III) and Cu(II) complexes of a novel alcohol and phenol cotaining polyamine ligand $H_{2}L$($H_{2}L$= N,N' -bis(2-hydroxybenzyl)-1,3-bis[(2-aminoethyl)amino]-2-propanol), Polyhedron, 24, 165-171
  18. Kim, S. D. and Y. S. Park, 2003, Synthesis of new $N_{2}O$ tridentate ligands and their stability constants of transition metal complexes, 47(6), 569-577
  19. Martell, A. E. and R. J. Motekaitis, 1992, 'Determination and use of stability constant', 2nd Ed. VCH, N. Y, pp.7-128
  20. Motekaitis, R. J. and A. E. Martell, 1992, Stabilities of metal complexes of the meso and ss isomers of oxylisuccinic acid, Inorg. Chem., 31, 11-15
  21. Parson, G. H. and C. H. Rochester, 1975, Acid ionization constants of 4-substituted phenols in methanol+water mixture, J. Chern. Soc. Faraday I, 71, 1058-1068
  22. Jerry, M., 1968, Advanced Organic Chemistry: Reactions, Mechanisms and Structure, McGraw Hill Book Company, New York, pp. 238-245
  23. Koseoglu, F., E. Kilic and D. Uysal, 1995, Protonation constants of some substituted 2-hydroxy-1-naphthalideneanilines in dioxan-water mixtures, Talanta, 42, 1875-1882
  24. Coleman, W. M., 1981, Relationships between ligand carbon-13 chemical shifts and reduction potentials of Mn(III) complexes, Inorg. Chim. Acta, 53, L191-L193
  25. Taylor, L. T. and W. M. Coleman, 1882, Copper(ll) complexes of tridentate schiff base ligand, Inorg. Chim. Acta, 63, 183-187