Electronic Structure and Electrochemistry of Complexes Trans-bis(tri-phenyl phosphine) Palladium(II) and Nickel(II) with Ligands $(CH_3COO-,\;Cl-\;and\;CO)$

리간드 $(CH_3COO-,\;Cl-,\;CO)$와 트란스-비스(트리페닐포스핀) 팔라듐(II) 과 니켈(II) 착물들에 대한 전자적구조와 전기화학적 연구

  • Choe Chil Nam (Department of Chemistry, Chosun University) ;
  • Jung Oh Jin (Department of Chemistry, Chosun University) ;
  • Kim Se Bong (Department of Chemistry, Chosun University)
  • Published : 1992.02.20

Abstract

The ability to account for magnetic and spectra properties of complexes was investigated for the splitting of the degenerate d-orbitals and with nonaqueous solution by UV/vis-spectrophotometric method. The correlation of the magnetitude of 10Dq obtained from the spectra, the pairing energy, and the spin state of the complexes. The electrochemical behavior of complexes were investigated by the use of cyclic voltammetry in aprotic media. These reduction peak of $[(C_6H_5)3_P]_2Pd(II)(CH_3COO)_2$ and $[(C_6H_5)_3Pd]_2Pd(II)Cl_2$ were irreversible one-electron processes at peak $E_{pc1} = -1.32 V,\;E_{pc2} = -1.56 V$ and $E_{pc1} = -1.74 V,\;E_{pc2} = -1.88 V$ of these complexes vs. Ag/AgCl, but nickel complexes were not to be reducible.

착물들의 자기성과 스펙트라의 성질은 d 궤도 함수의 퇴화에 대한 분열과 자외선 가시 분광학적 방법으로 비수용액 속에서 조사하였다. 10Dq의 에너지 크기는 착물들의 스펙트라와 결합에너지 그리고 스핀상태로부터 얻어졌다. 전기화학적 거동은 순환전압 전류법에 의해 측정하였다. 이들의 환원 피크는 Ag/AgCl 전극으로 20mV/s에서 $[(C_6H_5)3_P]_2Pd(II)(CH_3COO)_2$$E_{pc1} = -1.32 V,\;E_{pc2} = -1.56 V$이고, 그리고 $[(C_6H_5)_3Pd]_2Pd(II)Cl_2$에서는 $E_{pc1} = -1.74 V,\;E_{pc2} = -1.88 V$로 일전자 비가역적인 과정이었다. 그러나 $Ni^{2+}$ 착물에서는 환원성으로 되지 않았다.

Keywords

References

  1. Inorg. Chem. v.16 S. Kawaguch
  2. Inorg. Chem. v.17
  3. J. Chem. Soc. v.2 F. H. Jardine;D. H. Williamson
  4. J. Am. Chem. Soc. v.83 A. Wojcicki;F. Basolo
  5. Mechanisms of Inorganic Reaction F. Basolo;R. G. Pearson
  6. Adv. Organomet, Chem. v.17 B. R. James
  7. Inorg. Chem. v.18 W. M. Beck;J. C. Calabrese;N. D. Kottmair
  8. Inorg. Chem. v.2 G. S. Hamonond;D. C. Nonhebel;C. S. Wu
  9. Inorganic Chemistry J. E. Huheey
  10. Angew. Chem., Int. Ed. Engl. v.25 K. Wieghardt;H. J. Raabe;C. Kruger
  11. Bull. Chem. Soc., Japan. v.44 Y. Iida
  12. Basic Inorganic Chemistry F. A. Cotton;G. Wilkinsons
  13. J. Chem. Soc., Dalton Trans A. J. Hall;D. P. N. Satchell
  14. Inorganic Chemistry J. E. Huheey
  15. Comprehensive Coordination Chemistry v.1 R. D. Gillard;J. A. Mccleverty
  16. An Introduction to Coordination Chemistry D. P. Graddon
  17. Inorg. Chem. v.29 W. N. Setzer;D. G. Van Derveer
  18. Inorg. Chem. v.27 S. R. Cooper;S. C. Rawle;J. R. Hartman;E. J. Hintsa;G. A. Admans
  19. Inorg. Chem. v.30 Gregory J. Grant;Carolyn D. Grant;William N. Setzer
  20. Inorg. Chem. v.26 W. A. Nevin;M. R. Hempstead;W. Liu;C. C. Leznoff;A. B. P. Lever
  21. Inorg. Chem. v.28 R. O. Terrence;J. N. Toole;B. P. S. Yoounathan;J. M. Thomas