Applied Chemistry for Engineering (공업화학)

The Korean Society of Industrial and Engineering Chemistry (한국공업화학회)
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Synthesis of Transition Metal Cu(II) Complexes and Their Electrochemical Properties

Cu(II) 전이금속 착물의 합성과 전기화학적 성질에 관한 연구

  • Chae, Hee-nam (Department of Chemistry, Chonnam Nationnal University) ;
  • Choi, Yong-kook (Department of Chemistry, Chonnam Nationnal University)
  • 채희남 (전남대학교 자연과학대학 화학과) ;
  • 최용국 (전남대학교 자연과학대학 화학과)
  • Received : 1998.03.31
  • Accepted : 1998.06.02
  • Published : 1998.10.10
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Abstract

Tridentate Schiff base ligands were prepared by the reactions of salicylaldehyde and 2-hydroxy-1-naphthaldehyde with 2-aminophenol and 2-amino-p-cresol. And then Cu(II) complexes of those ligands were synthesized. The structures and properties of ligands and their complexes were studied by elemental analysis, $^1H$-NMR, IR, UV-visible spectra, and thermogravimetric analysis. The mole ratio of Schiff base to the metal of complexes was found to be 1:1. Cu(II) complexes were contemplated to be four-coordinated square planar configuration containing one water molecule. The redox process of ligands and complexes in DMSO solution containing 0.1 M TBAP as a supporting electrolyte was investigated by cyclic voltammetry and differential pulse voltammetry with glassy carbon electrode. The redox process of the tridentate Schiff base ligands was totally irreversible. The redox process of Cu(II) complexes was quasi-reversible and diffusion-controlled as one electron by one step process Cu(II)/Cu(I). The reduction potentials of the Cu(II) complexes shifted in the positive direction in the order of [Cu(II)(HNIPC)($H_2O$)]>[Cu(II)(HNIP)($H_2O$)]>[Cu(II)(SIP)($H_2O$)]>[Cu(II)(SIPC)($H_2O$)].

Salicylaldehyde와 2-hydroxy-1-naphthaldehyde를 2-aminophenol과 2-amino-p-cresol에 반응시켜 세자리 Schiff base 리간드들을 합성하였다. 이들 리간드를 Cu(II)이온과 반응시켜 세자리 Schiff base Cu(II) 착물들을 합성하였다. 리간드와 그 착물들의 구조와 특성을 원소분석, $^1H$-NMR, IR, UV-vis 분광법과 열 무게 분석법으로 알아보았다. Schiff base 리간드와 Cu(II)의 몰비는 1:1로 결합하며 Cu(II)착물들은 1 분자의 수화물이 배위된 4배위의 평면 사각형 구조임을 알았다. 지지전해질로서 0.1M TBAP를 포함한 DMSO 용액에서 순환 전압전류법과 미분 펄스 전압전류법으로 세자리 Schiff base 리간드와 이들의 Cu(II) 착물들의 전기 화학적인 산화 환원 과정을 알아보았다. 세자리 Schiff base 리간드들의 전기 화학적 환원은 확산 지배적이고 비가역적으로 진행되었다. Cu(II) 착물들의 전기화학적 환원과정은 1단계 1전자 반응으로 모두 확산 지배적이고 준가역적으로 진행되었다. Cu(II)착물들의 환원전위는 [Cu(II)(HNIPC)($H_2O$)]>[Cu(II)(HNIP)($H_2O$)]>[Cu(II)(SIP)($H_2O$)]>[Cu(II)(SIPC)($H_2O$)] 순으로 양전위 방향으로 이동하였다.

Keywords

Acknowledgement

Supported by : 교육부

References

  1. J. Chem. Ed. v.54 T. G. Appleton
  2. Top. Curr. Chem. v.121 J. E. Baldwin;P. Perlmutter
  3. Acc. Chem. Res. v.17 E. P. Guengerich;J. L. McDonald
  4. Oxygen Activation by Transition Metals A. E. Martell(ed.);D. T. Sawer(ed.)
  5. Inorg. Chem. v.32 C. P. Horwitz;P. J. Winslow;J. T. Warden;C. A. Lisek
  6. J. Chem. Soc. v.A C. Floriani;F. Calderazzo
  7. J. Chem. Soc. Dalton Trans. F. M. Ashmawy;C. A. McAuliffe;R. V. Parish;J. Tames
  8. Purification of Laboratory Chemicals(3rd ed.) D. D. Perrin;W. L. F. Armarego
  9. Inorg. Chem. v.10 W. M. Coleman;R. K. Boggess;J. W. Hughes;L. Taylor
  10. J. Chem. Phys. v.23 M. Kobayashi;J. Fujita
  11. J. Phys. Chem. v.60 K. Ueno;A. E. Martell
  12. J. Chem. Soc. Dalton Trans. A. A. Isse;A. Gennaro;E. Vianello
  13. J. Chem. Ed. v.60 G. A. Mabbott