Analytical Science and Technology (분석과학)

The Korean Society of Analytical Sciences (한국분석과학회)
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Synthesis of new N2O2 tetradentate ligands and the substituent effect on the stability constants of the transition metal complexes

새로운 산소-질소(N2O2)계 네 자리 리간드의 합성과 전이금속 착물 안정도상수에 대한 치환기 효과

  • Kim, Sun Deuk (Department of Chemistry and Applied Chemistry, Daegu University) ;
  • Jin, Gyoung Rok (Department of Chemistry and Applied Chemistry, Daegu University)
  • 김선덕 (대구대학교 자연과학대학 화학, 응용화학과) ;
  • 진경록 (대구대학교 자연과학대학 화학, 응용화학과)
  • Received : 2006.01.23
  • Accepted : 2006.02.27
  • Published : 2006.04.27
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Abstract

Hydrobromic acid salt of a $N_2O_2$ tetradentate ligand, N,N'-bis(2-hydroxybenzyl)-ethylene-diamine ($H-BHE{\cdot}2HBr$) was synthesized. $Br-BHE{\cdot}2HBr$, $Cl-BHE{\cdot}2HBr$, $CH_3-BHE{\cdot}2HBr$ and $CH_3O-BHE{\cdot}2HBr$ having Br, Cl, $CH_3$ and $CH_3O$ substituents at 5-position of the phenol group of $H-BHE{\cdot}2HBr$ were also synthesized. $Nap-BHE{\cdot}2HBr$ having naphthalen-2-ol instead of the phenol group was also synthesized. The potentiometry study in aqueous solution revealed that the proton dissociations of the synthesized ligands occurred in four steps and the order of the calculated overall proton dissociation constants (${\log}{\beta}_p$) of each ligand was Br-BHE < Cl-BHE < H-BHE < Nap-BHE < $CH_3$-BHE < $CH_3O$-BHE. The order showed a similar trend to that of Hammett substituent constants(${\sigma}_P$). The order of the stability constants (${\log}K_{ML}$) was CO(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II). The order in their stability constants (${\log}K_{ML}$) of each transition metal complex agreed well with that of the overall proton dissociation constants (${\log}{\beta}_p$).

새로운 산소-질소($N_2O_2$)계 네 자리 리간드 N,N'-bis(2-hydroxybenzyl)-ethylenediamine($H-BHE{\cdot}2HBr$)의 브롬산염을 합성하였다. 또한 $H-BHE{\cdot}2HBr$의 페놀기 5-위치에 치환기로 브롬, 염소, 메틸기 및 메톡시기를 가진 $Br-BHE{\cdot}2HBr$, $Cl-BHE{\cdot}2HBr$, $CH_3-BHE{\cdot}2HBr$ 및 $CH_3O-BHE{\cdot}2HBr$을 합성하였다. 그리고 페놀기 대신에 naphthalen-2-ol을 가진 $Nap-BHE{\cdot}2HBr$도 합성하였다. 합성된 리간드들의 양성자 해리는 수용액에서 전위차 적정한 결과 4 단계로 일어났으며, 계산된 각 리간드의 총괄 양성자 해리상수(${\log}{\beta}_p$) 값은 Br-BHE < Cl-BHE < H-BHE < Nap-BHE < $CH_3$-BHE < $CH_3O$-BHE의 순서로 Hammett 상수(${\sigma}_P$) 값의 순서와 비교적 같은 경향을 나타내었다. 전이금속(II) 이온들의 착물의 안정도상수(${\log}K_{ML}$) 값의 크기는 Co(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II)의 순서이었다. 또한 각 리간드들의 전이금속(II) 이온들의 착물 안정도상수(${\log}K_{ML}$) 값들의 크기 순서도 리간드의 총괄 양성자 해리상수(${\log}{\beta}_p$) 값과 서로 잘 일치하였다.

Keywords

References

  1. S. D. Kim, C. I. Song, J. K. Kim and J. S. Kim, J. Enviro. Sci., 13(9), 835(2004)
  2. T. A. Furtsch and L. T. Taylor, Inorg. Chim. Acta., 61, 211(1982) https://doi.org/10.1016/S0020-1693(00)89142-2
  3. S. D. Kim, Y. T. Shin and S. W. Park, Anal. Sci. Tech., 11(6), 440(1998)
  4. J. W. Kolis, D. E. Hamilton and N. K. Kildahl, Inorg. Chem., 18(7), 1826(1979) https://doi.org/10.1021/ic50197a022
  5. D. P. Freyberg. G. M. Mockler and E. Sinn, J.C.S. Dalton. Trans., 447(1976)
  6. H. K. Lin, X. Wang, X. C. Su. S. R. Zhu and Y. T. Chen, Trans. Met. Chem., 27, 384(2002) https://doi.org/10.1023/A:1015051002413
  7. S. D. Kim, K. H. Jang and J. K. Kim, J. Kor. Chem. Soc., 42(5), 539(1998)
  8. L. W. Yang, S. Liu, S. Weng, S. Rettig and C. Orvig, Inorg. Chem., 34, 2164(1995) https://doi.org/10.1021/ic00112a032
  9. E. Wong, S. Lin, T. Lugger, F. E. Hahn and C. Orvig, Inorg. Chem., 34, 93(1995) https://doi.org/10.1021/ic00105a018
  10. C. J. Bannochi and A. E. Martell, Inorg. Chem., 30, 1385(1991) https://doi.org/10.1021/ic00006a041
  11. R. J. Montekatis, A. E. Martell and D. A. Nelson, Inorg. Chem., 23, 73(1984)
  12. J. Aggett and R. A. Richadson, Anal. Chim. Acta., 51, 528(1970) https://doi.org/10.1016/S0003-2670(01)95753-8
  13. J. Aggett and R. A. Richadson, Anal. Chim. Acta., 50, 269(1970) https://doi.org/10.1016/0003-2670(70)80066-6
  14. J. Aggett., A. W. Khoo and R. A. Richadson, J. Inorg. Nucl. Chem., 43, 1867(1981) https://doi.org/10.1016/0022-1902(81)80400-9
  15. L. Canali and D. C. Sherrington, Chem. Soc. Rev., 28, 85(1999) https://doi.org/10.1039/a806483k
  16. T. Hashihayata, Y. Ito and T. Katsuki, Tetrahedron. 53, 9541(1997) https://doi.org/10.1016/S0040-4020(97)00633-9
  17. E. N. Jacobsen, F. Kakiuch, R. G. Konsler, J. F. Larrow and M. Tokunaga, Tetrahedron Lett., 38, 773(1997) https://doi.org/10.1016/S0040-4039(96)02414-8
  18. S. E. Schaus, J. Branalt and E. N. Jacobsen, J. Org. Chem., 63, 403(1998) https://doi.org/10.1021/jo971758c
  19. M. S. Sigman and E. N. Jacobsen, J. Am. Chem. Soc., 120, 5315(1998) https://doi.org/10.1021/ja980299+
  20. T. Katsuki, Coord. Chem. Rev., 140, 189(1995) https://doi.org/10.1016/0010-8545(94)01124-T
  21. R. J. Motekaitis and A. E. Martell, Inorg. Chem., 31, 11(1992) https://doi.org/10.1021/ic00027a004
  22. A. E. Martell and R. J. Motekatis, 'Determination and Use of Stability Constant', 2nd Ed. VCH, N. Y.(1992)
  23. A. C. Braithwaite, P. E. Wright and T. N. Waters, J. Inorg. Nucl. Chem., 37, 1669(1975) https://doi.org/10.1016/0022-1902(75)80295-8
  24. G. H. Parsons and C. H. Rochester, J. Chem. Soc. Faraday I, 71, 1058(1975) https://doi.org/10.1039/f19757101058
  25. A. J. Hoefnagel and B. M. Wepster, J. Chem. Soc. Perkin Trans. II, 977(1989)
  26. J. March, 'Advanced Organic Chemistry: Reactions, Mechanisms and Structure', MeGraw Hill Book Company, N. Y. 238-245(1968)
  27. F. Koseoglu, E. Kilic and D. Uysal, Talanta, 42, 1875(1995) https://doi.org/10.1016/0039-9140(95)01649-X
  28. F. Koseoglu, E. Kilic, E. Canel and N. Yilmaz, Anal. Chim. Acta., 293, 87(1994) https://doi.org/10.1016/0003-2670(94)00077-8
  29. W. M. Coleman, Inorg. Chim. Acta., 16(7), L191(1981) https://doi.org/10.1016/S0020-1693(00)91712-2