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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 30, Number 4
JKCSEZ 30(4)
August 20, 1986 

Racemization of Optical Active tris-Oxalatocobaltate (Ⅲ) Ion in Mixed Solvants

혼합용매내에서 광학활성인 tris-Oxalatocobaltate (Ⅲ) ion의 라세미화에 관한 연구
Dong-Jin Lee, Myung-Ki Doh

이동진, 도명기
광학활성인 Λ-[Co(ox)3]3+ ion을 이용하여 라세미체인 [Co(ox)3]3+ 이온을 광학분할한 후 얻어진 Λ-[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 ΔH≠와 ΔS≠를 고려하면 Λ-[Co(ox)3]3-의 라세미화메카니즘은 가능한 라세미화메카니즘중 twist메카니즘으로 진행됨을 알 수 있었다.

Racemic tris-oxalatocobaltate (Ⅲ) complex ions were optically resolved by an optical active complex, Δ-tris-ethylenediamine cobalt (Ⅲ), and then racemization of Λ-[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 ΔH≠, ΔS≠ and above facts for the racemization of Λ-[Co(ox)3]3-, it seems to be twist mechanism of plausible mechanisms.

377 - 382
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