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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 43, Number 2
JKCSEZ 43(2)
April 20, 1999 

 
Title
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
Author
Jung-Sung Kim, Jin-Tae Choi, Young-Dae Song, Tae-Sub Cho

김정성, 최진태, 송영대, 조태섭
Keywords
Abstract
Fe(II) 및 Ni(II) 이온에 NH3 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(H2O)6-x(NH3)x]2+(M=Fe(II), Ni(II)(x=0,1,…,6)에서 NH3 분자가 H2O 분자와 단계적으로 치환될 때에 따른 실측리간드화열이 MO 이론으로 계산한 팔면체형인 Fe(II)및 Ni(II)착물의 양자화학적 양인 중심금속의 알짜전하, 형성엔탈피, 총결합에너지로부터 실측 리간드화열(ΔHobs)을 이론적으로 예측할 수 있는 ΔHobs=-0.2858qFe+0.8813(r=0.97), ΔHobs=-0.8981qNi+1.7929(r=0.95), ΔHobs=-0.0031Hf(Fe)+0.5725(r=0.97), ΔHobs=-0.0095Hf(Ni)+0.9193(r=0.97), ΔHobs=0.0476Ediss(Fe)+0.6434(r=0.94), ΔHobs=0.1401Ediss(Ni)+1.1393(r=0.93)인 이론식을 각각 얻었다.

The correlation was investigated between the observed heat of ligation and calculated quantum chemical quantities for octahedral [M(H2O)6-x(NH3)x]2+ (M=Fe(II), Ni(II)) complexes by EHMO(Extended Huckel Molecular Orbital) and ZINDO/1(Zemer's Intermediate Neglected of Differential Overlap)method. The net charge of Fe2+ and Ni2+ ion of octahedral [M(H2O)6-x(NH3)x]2+(M=Fe(II), Ni(II)) complexes(x=O, 1, …, 6) decreased with substituting NH3 for H2O 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 ΔHobs=-0.2858qFe+0.8813(r=0.97), ΔHobs=-0.8981qNi+1.7929(r=0.95), ΔHobs=-0.0031Hf(Fe)+0.5725(r=0.97), ΔHobs=-0.0095Hf(Ni)+0.9193(r=0.97), ΔHobs=0.0476Ediss(Fe)+0.6434(r=0.94), ΔHobs=0.1401Ediss(Ni)+1.1393(r=0.93)

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