Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Racemization of Optical Active tris-Oxalatocobaltate (III) Ion in Mixed Solvants

혼합용매내에서 광학활성인 tris-Oxalatocobaltate (III) ion의 라세미화에 관한 연구

  • Dong Jin Lee (Department of Chemistry, College of Science Yeungnam University) ;
  • Doh Myung Ki (Department of Chemistry, College of Science Yeungnam University)
  • 이동진 (영남대학교 이과대학 화학과) ;
  • 도명기 (영남대학교 이과대학 화학과)
  • Published : 1986.08.20
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Abstract

Racemic tris-oxalatocobaltate (III) complex ions were optically resolved by an optical active complex, ${\Delta}$-tris-ethylenediamine cobalt (III), and then racemization of ${\bigwedge}-[Co(ox)_3]^{3-}$ obtained was investigated in various mixed solvent such as water-organic solvent (organic solvents=ethanol, iso-propyl alcohol, acetone, and dioxane). The rate of racemization was increased with following order; water < ethanol < acetone < isopropyl alcohol < dioxane; which is the same order for polarizability of organic solvent added. Considering ${\Delta}H^{\neq},\;{\Delta}S^{\neq}$ and above facts for the racemization of ${\bigwedge}-[Co(ox)_3]^{3-}$, it seems to be twist mechanism of plausible mechanisms.

광학활성인 ${\Delta}-[Co(en)_3]^{3+}$ion을 이용하여 라세미체인 $[Co(ox)_3]^{3-}$ 이온을 광학분할한 후 얻어진 ${\bigwedge}-[Co(ox)_3]^{3-}$ 이온의 라세미화를 여러가지 혼합용매 즉, 물-유기용매(유기용매=에탄올, 이소푸로필알코올, 아세톤 및 디옥산)내에서 조사하였다. 라세미화속도는 물<에탄올<이소프로필 알코올<디옥산의 순서로 증가하였고 그 순서는 첨가한 유기용매의 polarizability의 증가순서와 일치하였다. 이상의 결과와 ${\Delta}H^{\neq}$와 ${\Delta}S^{\neq}$를 고려하면 ${\bigwedge}-[Co(ox)_3]^{3-}$의 라세미화메카니즘은 가능한 라세미화메카니즘중 twist메카니즘으로 진행됨을 알 수 있었다.

Keywords

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