Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Physical Properties of Octahedral Iron (Ⅱ) Complexes of Vicinal-Dioximes

팔면체형 철 (Ⅱ) Vicinal-디옥심 착물의 물리적 성질

  • Chong-Shik Chin (Department of Chemistry, Sogang University) ;
  • L. Vaska (Department of Chemistry, Clarkson College of Technology)
  • 진종식 (西江大學校 理工大學 化學科) ;
  • Published : 1980.10.30
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Abstract

Six coordinate low spin iron(Ⅱ) complexes of vicinal-dioximes, [Fe$(DH)_2B_2$] and [Fe$(DH)_2$B(CO)]($(DH)_2$=$(CHDH)_2$(bis(1,2-cyclohexadinedioximato) bivalent anion), $(DPGH)_2$-(bis(diphenylglyoximato) bivalent anion), $(F{\alpha}DH)_2(bis(furil-{\alpha}-dioximato)$ bivalent anion); B = monodentate neutral nitrogen base), have been prepared and their physical properties have been investigated with respect to the effects of the equatorial ligands, $(DH)_2$. The order of ${\pi}$-acceptor CO stretching frequency for [Fe$(DH)_2$B(CO)] is $(F{\alpha}DH)_2$ > $(DPGH)_2$> $(CHDH)_2$, while non-${\pi}$-acceptor $NH_3$ stretching frequencies for [Fe$(DH)_2(NH_3)_2$] show the opposite order to that of CO, i.e., $(CHDH)_2$ > $(DPGH)_2$ > $(F{\alpha}DH)_2$. These infrared spectral data together with Fe-N (oxime) and Fe-N (oxime) and Fe-N (B) stretching frequency data suggest that the nitrogen atoms of $(CHDH)_2$ are more basic and poorer ${\pi}$-acceptors than the corresponding nitrogen atoms of $(DPGH)_2$ and $(F{\alpha}DH)_2$, respectively. It has been found from the electronic spectral data of [Fe$(DH)_2$] and [Fe$(DH)_2$B(CO)] that the energy of the charge transfer band from iron(Ⅱ) to $(DH)_2$ increases as the basicity of $(DH)_2$ increases.

6배위, 작은 스핀 철(Ⅱ)착화합물, [Fe$(DH)_2B_2$]과 [Fe(D$H_2$B(CO)]($(DH)_2$=$(CHDH)_2$-(bis(1,2-cyclohexadinedioximato)(bivalent anion),$(DPGH)_2$(bis(diphenylglyoximato) bivalent anion), $(F{\alpha}DH)_2(bis(furil-{\alpaha}$-dioximato) bivalent anion), B = neutral monodentate nitrogen base)을 합성하여 이들의 물리적 성질을 적도 방향의 리간드, $(DH)_2$에 관하여 조사하였다. 적외선 스펙트럼 분석결과, [Fe$(DH)_2B(CO)] 중에서 {\pi}$-전자받게 리간드인 CO의 신축진동수 크기의 순서는 $(F{\alpha}DH)_2$ > $(DPGH)_2$ > $(CHDH)_2 화합물의 순서이고 [Fe$(DH)_2(NH_3)_2$]중에서 ${\pi}$-전자받게 성질이 없는 $NH_3$의 신축진동수 크기의 순서는 그 반대인 $(CHDH)_2$ > $(DPGH)_2 > $(F{\alpha}DH)_2$ 화합물임을 관찰하였다. 이상의 결과와 철-질소(옥심) 및 철-질소(B)의 신축진동수 데이타로부터 다음을 알았다. 즉 $(CHDH)_2$중의 질소원자들은 $(DPGH)_2$ 및 $(F{\alpha}DH)_2$ 중의 질소원자들보다 염기도는 크지만 ${\pi}$-전자받게의 경향은 적다. 상기 착물들의 전자스펙트럼을 조사한 결과 $(DH)_2의 염기도가 증가함에 따라 철로부터 $(DH)_2$로 일어나는 전하이동띠의 에너지가 증가함을 알았다.

Keywords

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