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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

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【作者】 徐志固; 俞鼎琼;

【Author】 Xu Zhigu Yu Dingqiong (Department of Chemistry, Xiamen University, Fujian)

【机构】 厦门大学化学系; 厦门大学化学系 福建; 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]的四种对映体在1.56×10-2M HClO4介质和中性水溶液中的异构化外消旋反应的产物用Na+型SP-Sephadex C-25柱分离后,用分光光度法和旋光仪测定了它们的浓度和旋光度。实验结果表明,这些对映体的异构化外消旋反应比较可能是按Werner首先提出的断键-分子内重排的机理进行。机理研究正在深入进行。

【Abstract】 The complete resolution of 1.0g fac-[Co(β-ala)s] [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 HC104 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.

【基金】 中国科学院科学基金资助课题
  • 【文献出处】 无机化学学报 ,Chinese Journal of Inorganic Chemistry , 编辑部邮箱 ,1988年03期
  • 【下载频次】55
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