Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Synthesis of Cobalt(II), Nickel(II) and Copper(II) Complexes with Tetradentate Schiff Base Ligand of o-BSDT $H_2$ and Electrochemical properties in DMSO

네자리 Schiff Base 리간드의 Cobalt(II), Nickel(II) 및 Copper(II) 착물의 합성과 DMSO용액에서 전기화학적 성질

  • Ki-Hyung Chjo (Department of Chemistry, Chonnam National University) ;
  • Jong-Soon Kim (Department of Chemistry, Chonnam National University)
  • 조기형 (전남대학교 자연과학대학 화학과) ;
  • 김종순 (전남대학교 자연과학대학 화학과)
  • Published : 1987.12.20
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Abstract

The tetradentate Schiff base ligand, 3,4-bis(salicylidene diimine) toluene, have been prepared by the reaction of salicylaldehyde with 3,4-diaminotoluene by Duff method. The Schiff base ligand reacts with Ni(II), Co(II), and Cu(II) ions to form new complexes, [Ni(o-BSDT)${\cdot}(H_2O)_2$], [Co(o-BSDT)${\cdot}(H_2O)$], and [Cu(o-BSDT)]. It seems that Ni(II) and Ni(II) complexes are hexacoordinated with the Schiff base ligand and two molecules of water, while the Cu(II) complexes are tetracoordinated with the Schiff base. The mole ratio of tetradentate Schiff base ligand to metals was found to be 1 : 1. The redox chemistry of these complexes was investigated by polarography and cyclic voltammetry with glassy carbon electrode in DMSO with 0.1M TEAP${\cdot}$[Ni(o-BSDT)${\cdot}(H_2O)_2$] hav EC reaction mechanisms which undergo a irreversible electron transfer followed by a fast chemical reaction. [Co(o-BSDT)${\cdot}(H_2O)_2$] undergoes a reduction of Co(II) to Co(I) and a oxidation of Co(II) to Co(III), and [Cu(o-BSDT)] undergoes a reduction of Cu(II) to Cu(I).

네자리 Schiff base 리간드인 3,4-bis(salicylidene diimine) toluene [o-BSDT $H_2$]를 salicylaldehyde에 3,4-diaminotoluene를 Duff 반응시킴으로써 합성하였으며 이들 리간드와 Ni(II), Co(II) 및 Cu(II)이온들과의 새로운 착물 [Ni(o-BSDT)${\cdot}(H_2O)_2$], [Co(o-BSDT)${\cdot}(H_2O)_2$] 및 [Cu(o-BSDT)]를 합성하였다. 이들 착물에 대한 원소분석, 전자흡수스펙트럼, 적외선 스펙트럼 및 T.G.A. 측정결과에 의하여 Ni(II)와 Co(II) 착물은 리간드대 금속이 1 : 1 몰비의 4배위 착물임을 알았다. 0.1M TEAP-DMSO 용액에서의 폴라로그래피와 순환전압-전류법을 조사한 결과 [Ni(o-BSDT)${\cdot}(H_2O)_2$]는 비가역적인 electron transfer 다음에 빠른 화학적 반응을 하는 EC반응기구를 보이며 [Co(o-BSDT)${\cdot}(H_2O)_2$]는 Co(II) - Co(I)로의 환원과 Co(II) - Co(III)로의 산화가 일어나며, [Cu(o-BSDT)]착물은 Cu(II) - Cu(I)로의 환원이 일어남이 밝혀졌다.

Keywords

References

  1. J. Pract. Chem. P. Pfeiffer(et al.)
  2. J. Chem. Soc. Japan v.74 M. Yamaguchi
  3. Bull. Chem. Soc. Japan v.33 no.9 Y. Muto
  4. Bull. Chem. Soc. Japan v.46 H. Okawa;T. Tokii;Y. Muto;S. Kida
  5. Bull. Chem. Soc. Japan v.46 H. Okawa;T. Tokii;Y. Muto;S. Kida
  6. J. Chem. Soc. Korea v.18 no.4 K. H. Chj
  7. J. Chem. Soc. Korea v.18 no.3 K. H. Chjo
  8. J. Nat. Sci. (Chonnam univ.) v.8 no.1 K. H. Chjo
  9. J. Nat. Sci. (Chonnam univ.) v.7 no.1 K. H. Chjo
  10. J. Nat. Sci. (Chonnam univ.) v.10 no.1 K. H. Chjo
  11. Inorg. Chem. v.8 D. C. Olson;J. Vasilevskis
  12. Inorg. Chem. v.10 D. C. Olson;J. Vasilevskis
  13. Inorg. Chem. v.10 J. Vasilevskis;D. C. Olson
  14. Bull. Chem. Soc. Japan v.45 Kodama, Y. Fujii;M. Sakurai
  15. Bull. Chem. Soc. Japan v.48 M. Kodama
  16. Inorg. Chem. v.17 D. F. Averill;R. F. Broman
  17. Inorg. Chem. v.20 W. M. Coleman;R. K. Boggess;J. W. Hughes;L. T. Taylor
  18. Inorg. Chem. v.20 W. M. Coleman;R. K. Boggess;J. W. Hughes;L. T. Taylor
  19. Inorg. Chem. v.23 J. R. Bradbury;G. R. Hanson;A. M. Bond;A. G. Wedd
  20. Inorg. Chem. v.17 J. J. Grazybowski;P. H. Merrell;F. L. Urach
  21. J. Am. Chem. Soc. v.100 D. E. Fenton;R. L. Lintvedt
  22. J. Am. Chem. Soc. v.101 R. R. Gagne;C. A. Koval;T. J. Smith;M. C. Cimolino
  23. J. Am. Chem. Soc. v.103 R. R. Gagne;C. L. Spiro;T. J. Smith;C. A, Hamann;W. R. Thies;A. K. Shiemke
  24. J. Am. Chem. Soc. v.105 R. C. Long;D. N. Hendrickson
  25. J. Am. Chem. Soc. v.105 R. S. Drago;M. J. Desmond;B. B. Corden;K. A. Miller
  26. Inorg. Chem. v.24 W. Mazurek;A. M. Bond;K. S. Murray;M. J. O'Connor;A. G. Wedd
  27. J. Chem. Soc. J. C. Duff
  28. chelate 滴定法 上野景平者
  29. The infrared Spectra of Complex Molecules I. J. Bellamy
  30. J. Am. Chem. Soc. v.71 R. S. Rasmussen;D. D. Tunnicliff;R. R. Brattain
  31. J. Phys. Chem. v.60 K. Ueno;A. E. Martell
  32. J. Chem. Phys. v.22 D. G. Hill;A. F. Rosenberg
  33. J. Chem. Phys. v.24 D. G. Hill;A. F. Rosenberg
  34. J. Chem. Phys. v.23 K. Kobayashi;J. Fujita
  35. J. Chem. Phys. v.32 K. Nakamoto;A. E. Martell
  36. J. Am. Chem. Soc. v.83 K. Nakamoto;P. J. Mc Carthy;A. Rudy;A. E. Martell
  37. J. Phys. Chem. Ithaca v.66 K. Nakamoto;Y. Morimeto;A. E. Martell
  38. J. Am. Chem. Soc. v.91 R. S. Downing;F. L. Urbach
  39. Inorg. Chem. v.13 I. E. Dickson;R. Robson
  40. Inorg. Chem. v.23 W. Mazurek;K. J. Berry;K. S. Murray;M. J. O'Connor;M. R. Snow;A. G. Wedd
  41. Laboratory Technigues in Electroanalytical Chemistry P. T. Kissinger;W. R. Heineman