Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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The Electronic Structure and Reactivity of Transition Metal Complexes (II). Molecular Orbital Studies of the Series $[M(NH_3)_5Cl]^{2+}$ (M = Cr, Co, Ru, Rh, Os, Ir) by the Relativistically Parameterized Extended Huckel Method

전이금속 착물의 전자구조 및 화학적 반응성 (제 2 보). 상대론적으로 파라미터화된 확장 Huckel 법에 의한 $[M(NH_3)_5Cl]^{2+}$ (M = Cr, Co, Ru, Rh, Os, Ir) 계열의 분자궤도함수론적 연구

  • Jong-Jae Chung (Department of Chemistry, Kyungpook National University) ;
  • Hwan-Jin Yeo (Department of Chemistry, Kyungpook National University) ;
  • Jong-Ha Choi (Department of Chemistry, Andong National University) ;
  • Iee-Yeung Cho (Department of Chemistry, Kyungpook National University)
  • Published : 1989.12.20
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Abstract

The relativistically parameterized Extended Huckel (REX) calculations are carried out for $[M(NH_3)_5Cl]^{2+}$ (M = Cr, Co, Ru, Rh, Os, Ir). The calculated orbital and overlap populations agree with experimental data. The REX calculations on the electronic structure have been also compared with nonrelativistic EHT results. A ${\phi}$-bonding in M-Cl bond is founded to be more important for the $d^3$, $d^5$complexes than the $d^6$ system.

$[M(NH_3)_5Cl]^{2+}$착물에 대하여 상대론적으로 파라미터화된 확장 Huckel(REX) 계산을 수행하였다. 궤도함수 및 overlap population에 대한 계산 결과는 실험적인 자료와 일치하였다. 또한 전자구조에 대하여 상대성 효과를 감안한 REX와 비상대론적인 EHT의 계산 결과를 서로 비교하였다. 이들 착화합물의 M-Cl 결합에 대한 파이 결합성은 $d^6$계 착물에서 보다 $d^3$ 및 $d^5$계 착물의 경우가 더 중요함을 알 수 있었다.

Keywords

References

  1. Mechanisms of Inorganic Reactions F. Basolo;R. G. Pearson
  2. Inorganic Electronic Spectroscopy A. B. P. Lever
  3. Concept of Inorganic Photochemstry A. W. Adamson(ed.);P. D. Fleischauer(ed.)
  4. Inorg. Chem. v.21 R. L. Carlim;R. Burriel;K. R. Sedden;R. I. Crisp
  5. Inorg. Chem. v.25 T. W Hambley;P. A. Lay
  6. J. Chem. Phys. v.27 K. Nakamoto;J. Fujita;M. Kobayashi;R. Tsuchida
  7. J. Chem. Phys. v.20 M. Wolfsberg;L. Helmholz
  8. J. Basic Sciences v.7 Young-Hi Kwon
  9. J. Am. Chem. Soc. v.103 M. J. Ondrechen;M. A. Ratner;D. E. Ellis
  10. J. Chem. Soc. Dalton J. N. Murrell;A. Al-Derzi;G. J. Leigh;M. F. Guest
  11. Adv. Quantum Chem. v.11 P. Pyykko
  12. QCPE v.12 L. L. Lohr Jr.;M. Hotokka;P. Pyykko
  13. Method in Computational Chemistry v.2 P. Pyykko
  14. Chem. Phys. Lett. v.62 L. L. Lohr Jr.;Pyykko
  15. The 3-j and 6-j Symbols M. Rotenberg;J. Bivins;N. Metropolis;J. K. Wooten Jr.
  16. Theory of Transition Metal Ions J. S. Griffith
  17. At. Data Nucl. Data Tables v.12 J. P. Desclaux
  18. J. Chem. Phys. v.39 R. Hoffmann
  19. J. Chem. Phys. v.43 R. G. Hayes;N. Edelstein
  20. Inorg. Chem. v.19 K. Tatsumi;R. Hoffmann
  21. Int. J. Quantum Chem. Symp. v.20 E. A. boudreaux;S. P. Doussa;M. Klobukowski
  22. Acc. Chem. Res. v.12 P. Pyykko;J. P. Desclaux
  23. J. Am. Chem. Soc. v.108 N. Koga;K. Morokuma
  24. Mol. Phys. v.50 W. H. E. Schwartz;S. Y. Chu;F. Mark
  25. Chem. Rev. v.88 P. Pyykko