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化学学报
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化学学报 ›› 1981, Vol. 39 ›› Issue (5): 453-460. 上一篇    下一篇

论文

气相色谱法研究稀土金属络合物的络合作用——Ⅰ.三-[1,1,1,2,2,3,3-七氟-7,7-二甲基-辛二酮-(4,6)]铕(Ⅲ)与醚类的相互作用

厐廷斌, 叶常青, 李玉琴, 钱长涛   

  1. 中国科学院上海有机化学研究所
  • 投稿日期:1979-08-02 发布日期:2013-06-03

GAS-CHROMATOGRAPHIC STUDIES ON THE COMPLEXATION INTERACTION OF RARE EARTH COMPLEXES Ⅰ. THE INTERACTION OF TRIS (1, 1, 1, 2, 2, 3, 3-HEPTAFLUORO-7, 7-DIMETHYL-4, 6-OCTANEDIONATO)-EUROPIUM (Ⅲ) WITH ETHERS

PANG TING-BIN, YE CHANG-QING, LI YU-QIN, QIAN CHANG-TAO   

  1. Shanghai Institute of Organic Chemistry, Academia Sinica
  • Received:1979-08-02 Published:2013-06-03

PDF

756

被引次数

4

以三-[1,1,1,2,2,3,3-七氟-7,7-二甲基-辛二酮-(4,6)]铕(Ⅲ)[Eu(fod)3]在角鲨烷中的溶液作为气相色谱固定相,研究了电子效应和位阻效应对不同醚类与Eu(fod)3络合作用的影响。我们发现饱和脂肪醚与Eu(fod)3络合,位阻效应是主要因素。位阻越大,络合作用越弱,生成的络合物越不稳定。α-位不饱和脂肪醚及芳香醚,由于π键的共轭效应大大降低了氧原子的电子云密度,以致不易与Eu(fod)3络合,这时电子效应是主要因素。这些结果与酮、醇和Eu(fod)3的络合作用有所不同。

Tris(1, 1, 1, 2, 2, 3, 3-heptafluoro-7, 7-dimethyl-4, 6-octanedionato) europium-(Ⅲ),Eu(fod)3, in squalane solution was usod as the stationary phase in gas-chroma-tographic investigation of the interaction between various ethers and Eu (fod)3. It is found that the sterio hindrance plays an important role in the interaction of the saturated alkyl ethers with Eu(fod)3.In the case of saturated alkyl ethers, the greater the sterio hindrance, the less stable aro the complexes formed and the weaker is the interaction. Whereas in the a-unsaturated alkyl ethers and aryl ethers, owing to the conjugation effect of the π-bond which excessively dcoreases the electron density around the oxygen atom, the interaction becomes less easy a,nd the eleotronic effect becomes the prinoipal factor.These results are different from tliose of the interaotion of ketonea and alcohola with Eu(fod)3.