Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
권호 표지

Theoretical Study on Observed Heat of Ligation for Iron(Ⅱ) and Nickel(Ⅱ) Octahedral Complexes

팔면체형 Fe(Ⅱ)와 Ni(Ⅱ)착물의 실측 리간드화열에 관한 이론적 연구

  • 김정성 (대구대학교 사범대학 화학교육과) ;
  • 최진태 (대구대학교 사범대학 화학교육과) ;
  • 송영대 (영남대학교 이과대학 화학과) ;
  • 조태섭 (영남대학교 이과대학 화학과)
  • Published : 19990400
Download PDF
⟨ Previous Next ⟩

Abstract

The correlation was investigated between the observed heat of ligation and calculated quantum chemical quantities for octahedral $[M(H_2O)_{6-x}(NH_3)_x]^{2+} (M=Fe(II),\;Ni(II))$ complexes by EHMO(Extended Huckel Molecular Orbital) and ZINDO/1(Zerner's Intermediate Neglected of Differential Overlap)method. The net charge of $Fe^{2+}$ and $Ni^{2+}$ ion of octahedral $[M(H_2O)_{6-x}(NH_3)_x]^{2+}(M=Fe(II),\;Ni(II))$ complexes(x=O, 1, …, 6) decreased with substituting $NH_3$ for $H_2O$ molecules. It has found that a good correlation exists between the observed heat of ligation and the calculated quantum chemical quantities such as net charge of central atom, enthalpy of formation, and total dissociation energy. From this finding, we have obtained the following semiempirical linear equation ${\Delta}H_{obs}=-0.2858_{qFe}+0.8813(r=0.97),\;{\Delta}H_{obs}=-0.8981_{qNi}+1.7929(r=0.95),\;{\Delta}H_{obs}=-0.0031H_{f(Fe)}+0.5725(r=0.97),\;{\Delta}H_{obs}=-0.0095H_{f(Ni)}+0.9193(r=0.97),\;{\Delta}H_{obs}=0.0476E_{diss(Fe)}+0.6434(r=0.94),\;{\Delta}H_{obs}=0.1401E_{diss(Ni)}+1.1393(r=0.93)$.

Fe(II) 및 Ni(II) 이온에 $NH_3$ 리간드를 배위시켜 분자역학(MM2)법으로 최소에너지를 갖는 구조를 구한 후 확장분자궤도함수(EHMO)법 및 ZINDO/1법으로 양자화학적 양을 얻어 실험적 사실과 비교 검토하였다. 즉, 팔면체인 $[M(H_2O)_{6-x}(NH_3)_x]^{2+}(M=Fe(II),\;Ni(II)(x=0,\;1,\;…,\;6)에서 $NH_3$ 분자가 $H_2O$ 분자와 단계적으로 치환될 때에 따른 실측리간드화열이 MO 이론으로 계산한 팔면체형인 Fe(II)및 Ni(II)착물의 양자화학적 양인 중심금속의 알짜전하, 형성엔탈피, 총결합에너지로부터 실측 리간드화열$({\Delta}H_{obs})$을 이론적으로 예측할 수 있는 ${\Delta}H_{obs}=-0.2858_{qFe}+0.8813(r=0.97),\;{\Delta}H_{obs}=-0.8981_{qNi}+1.7929(r=0.95),\;{\Delta}H_{obs}=-0.0031H_{f(Fe)}+0.5725(r=0.97),\;{\Delta}H_{obs}=-0.0095H_{f(Ni)}+0.9193(r=0.97),\;{\Delta}H_{obs}=0.0476E_{diss(Fe)}+0.6434(r=0.94),\;{\Delta}H_{obs}=0.1401E_{diss(Ni)}+1.1393(r=0.93)$인 이론식을 각각 얻었다.

Keywords

References

  1. Structure and Bonding v.12 Smith, D. W.
  2. Structure and Bonding v.57 Hathaway, B. J.
  3. Comprehensive Coordination Chemistry v.5 Hathaway, B. J.;Wilkison, G.;Gillard, R. G.;McCleverty. J. A.
  4. Prog. Inorg. Chem v.1 George, P.;McClure,D. S.
  5. Introduction to Transition Metal Chemistry v.84 Orgel, L. E.
  6. Introduction to Ligand Field(2nd ed.) v.74 Figgis, B. N.
  7. Inorg. Chem. v.5 Elliott, H.;Hathaway, B. J.
  8. Acta. Chem. Scand. v.20 Roos, B.
  9. Inorg. Chem. v.5 Smith, D. W.
  10. J. Chem. Soc.(A) v.6 Smide, D. W.
  11. J. Chem. Soc.(A) v.3
  12. Inorg. Chem. Acta v.1 Shupack, S. I.
  13. J. Am. Chem. Soc. v.85 Gray, H. B.;Ballhausen, C. J.
  14. Inorg. Chem. v.6 Cotton, F. A.;Harris, C. B.;Wise, J. J.
  15. Inorg. Chem. v.34 Gomezgarcia, C. J.;Gimenizsaiz, C.;Triki, S.;Coronado, E.;Lemagueres, P.;Ouahab, L.;Ducasse, L.;Sourisseau, C.;Delhaes, P.
  16. J. Chem. Phys. v.20 Wolfsberg, M.;Helmholtz, L.
  17. J. Chem. Phys. v.36 Hoffmann, R.;Lipscomb, W. N.
  18. J. Chem. Phys. v.37 Hoffmann, R.;Lipscomb, W. N.
  19. J. Chem. Phys. v.39 Hoffmann, R.
  20. J. Am. Chem. Soc. v.117 Dibella, S.;Fragala, I.;Ledoux, I.;Marks, T. J.
  21. Theor. Chem. Acta. v.53 Zerner, M. C.;Bacom, A. D.
  22. Inorg. Chem. v.28 Angerson, W. P.;Edwards, W. D.;Zerner, M. C.
  23. Int. J. Quantum. Chem. v.39 Angerson, W. P.;Cundar, T. R.;Zerner, M. C.
  24. Inorg. Chem. v.23;24 Deeth, R. J.;Gerloch, M.
  25. J. Chem. Soc. Dalton Trans. v.S1 Orpen, A. G.;Brammer, L.;Allen, F. H.;Kennard, O.;Watson, D. G.;Taylor, R.
  26. J. Chem. Soc. Dalton Trans. no.11 Tables of Interatomic Distances and Configuration in Molecules and Ions Sutton, L. E.
  27. International Tables for X-ray Crystallography v.3 Kennard, O.
  28. Introduction to Ligand Field v.87 Figgis, B. N.
  29. Am. Chem. Soc. v.177 Molecular Mechanics, ACS Monography Burket, U.;Allinger, N. L.
  30. Used or MMX molecular mechanics calculations MMX program (a variant of MM2)
  31. J. Am. Chem. Soc. v.100 Ammeter, J. H.;Burg, H. B.;Thibwault, J. C.;Hoffmann, R.
  32. QCPE. v.11 Hoffmann, R.
  33. Hyperchem Package Copyright HyperCube, Inc
  34. Inorg. Chem. v.5 Elliott, H;Hathaway, B. J.;Slade, R. C.