光学活性配合物的合成、拆分和性能研究——Ⅲ.fac-、mer-〔Co(β-ala)3〕的手性固定相拆分和其对映体的异构化外消旋反应机理
STUDIES ON OPTICALLY ACTIVE METAL COMPLEXES——Ⅲ. RESOLUTION OF fac- AND mer- [Co(β-ala)3] WITH CHIRAL STATIONARY PHASE AND MECHANISM OF ISOMERIZATION-RACEMIZATION OF THEIR ENANTIOMERS
作者单位
徐志固 厦门大学化学系, 福建 
俞鼎琼 厦门大学化学系, 福建 
摘要: 本文用QAE-Sephadex-Sb2(d-tart)22-为手性交换固定相,50%乙醇水溶液为淋洗剂,在柱尺寸为80cm×2.2cm,淋洗速度为5.0ml/20min下完全拆分了1.0g fac-[Co(β-ala)3];用同一手性固定相和淋洗剂在淋洗速度为1.2ml/20min下mer-[Co(β-ala)3]的拆分量可增至0.78g。 fac-、mer-[Co(β-ala)3
关键词: fac-、mer-〔Co(β-ala)3〕的拆分  手性固定相  fac-、mer-〔Co(β-ala)3〕的对映体  异构化外消旋反应机理
基金项目: 中国科学院科学基金资助课题
Abstract: The complete resolution of 1.0g fac-[Co(β-ala)3] [is achieved with QAE-Sephadex A-25-Sb2(d-tart)22- as chiral stationary phase. The column size is 80 cm×2.2 cm; the eluent is 50% ethanol-water solution and the elution rate is 5.0 ml/20 min. Using the same stationary phase and eluent but at elution rate of 1.2 ml/20 min, the amount of resolution of mer-[Co(β-ala)3] is increased to 0.78g.The isomerization-racemization products of the four enantiomers of fac- and mer-[Co(β-ala)3] in both 1.56×10-2M HClO4 solution and neutral solution are separated by chromatographic method with Na+-type SP-Sephadex C-25 column and characterized by spectrophotometric and po-larimetric methods. The experimental results seem to conform the mechanism, first suggested by A. Werner, which suggests that isomerization and racemization of these enantiomers proceed by the path of bond rupture-intramolecular rearrangement. Further study on mechanism of iso-merization-racemization of these neutral complexes is in progress.
Keywords: resolution of fac- and mer-[Co(β-ala)3]  chiral stationary phase  enantiomers of fac- and mer-[Co(β-ala)3]  mechanism of iso-merization-racemization
投稿时间:1987-04-27 
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徐志固,俞鼎琼.光学活性配合物的合成、拆分和性能研究——Ⅲ.fac-、mer-〔Co(β-ala)3〕的手性固定相拆分和其对映体的异构化外消旋反应机理[J].无机化学学报,1988,4(3):28-33.
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