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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 25, Number 5
JKCSEZ 25(5)
October 20, 1981 

Induced Circular Dichroism Spectra and Chromatography by Interaction of Some Racemic Cobalt (Ⅲ) Complexes and d-Tartrate2- in Aqueous Solution

d-주석산이온과 라세미코발트(Ⅲ) 착물과의 상호작용에 따른 유발원편광이색성 Spectra와 크로마토그래피
Chang Eon Oh, Dae Ho Kang, Gab Choul Shin

오창언, 강대호, 신갑철
라세미코발트(Ⅲ)착물인 [Co(en)3]3+, [Co(tn)3]3+, cis-[Co(NH3)(en)2]3+[Co(β-ala)(en)2]2+, [Co(gly)(en)2]2+ 및 [Co(acac)(en)2]2+을 실온에서 d-주석산염의 수용액에 녹여 원편광이색성 spectra를 측정하였다. 측정된 모든 착물에 대해서 가시부영역 (400∼500nm)에 한개의 음의 CD spectrum이 관측되었다. 이것은 d-주석산이온과 Λ-및 Δ-거울상이성질체의 상호작용에 대한 차에의한 것이라고 해석되었다. 즉 Λ-및 Δ-거울상이성질체에 d-주석산이온을 각각 부가했을때 Λ-거울상이성질체는 크게 변하였고 Δ-거울상이성질체는 약하게 변하여 그 결과 유발원편광이색성 spectrum으로 나타났다. 이온교환 관크로마토그래피에 있어서 용리제와 더 강하게 회합하는 거울상이성질체가 관으로부터 더 빨리 용출된다. 만일 chiral음이온과 착물과의 더 강한 상호작용이 착물의 원래 부호로부터 크로마토그래피의 용리순서를 예측할 수가 있고, 실험결과 용리순서는 측정된 모든 착물에 대하여 유발 원편광이색성 spectrum의 부포로부터 예측된 거울상이성질체의 절대구조와 완전히 일치하였다.

Induced circular dichroism spectra of racemic cobalt(Ⅲ) complexes for [Co(en)3]3+, [Co(tn)3]3+, cis-[Co(NH3)(en)2]3+[Co(β-ala)(en)2]2+, [Co(gly)(en)2]2+ and [Co(acac)(en)2]2+ were measured when they were dissolved in aqueous d-tartrate2- solution at room temperature. Only a single negative CD spectrum was observed for all the complexes above in visible region(400∼500nm). It was interpreted that these CD bands were attributed to the difference in interaction between Λ-and Δ-enantiomers with d-tartrate2-. Namely, when d-tartrate2- was added to Λ-enantiomer and Δ-enantiomer, it caused Λ-enantiomer to change greatly and Δ-enantiomer to change only slightly; combined the results proved induced circular dichroism. The enantiomer for which the eluent has a stronger affinity should be eluted faster in ion-exchange column chromatography. It is possible to predict the elution order of chromatography from the sign of the induced CD if stronger interaction of chiral anion with the complex leads to greater change in the natural CD spectrum of the complex. The elution order was in complete agreement with the prediction from the sign of the induced CD spectrum for all the measured complexes.

306 - 310
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