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化学学报
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化学学报 ›› 1992, Vol. 50 ›› Issue (3): 262-268. 上一篇    下一篇

研究论文

[Co(tp)~2(Me-en)]ClO~4配合物不对称氮的翻转及重氢化动力学研究

马桂林;黄明昌   

  1. 扬州师范学院化学系
  • 发布日期:1992-03-15

The kinetic studies on inversion and deuteration at the chiral nitrogen center of [Co(tp)~2(Me-en)]^+

MA GUILIN;HUANG MINGCHANG   

  • Published:1992-03-15

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本文合成了[Co(tp)~2(Me-en)]ClO~4(tp:2-羟基-2,4,6-环庚三烯-1-酮负离子;Me-en:N-甲基乙二胺)三元不对称配合物, 用离子交换法分离了该配合物的Λ(R)△(S)和Λ(S)△(R)两对对映体, 用高效液相色谱法测定了对映体的不对称配位氮的翻转速率常数k~e~p(差向立体异构化速率常数), 用^1HNMR法测定了对映体的不对称配位氮的重氢化质子交换)速率常数k~D, 并与同属CoO~4~2型的Na[Co(OX)~2(Me-en)](OX:草酸根)、[Co(acac)~2(Me-en)]ClO~4(acac:2,4-戊二酮负离子)配合物的k~e~p、k~D值进行了比较, 讨论了影响质子交换、不对称氮翻转速率的因素及反应机理。

关键词: 反应机理, 反应动力学, 高速液体色谱, 离子交换, 核磁共振谱法, 三元络合物, 对映体, 钴络合物, 高氯酸盐, 反应速度

[Co(tp)2(Me-en)]ClO4 (Htp = tropolone, Me-en = N-methylethylenediamine) was prepared and L(R)D(S) and L(S)D(R) epimers were separated by ion exchange. Rates of base catalyzed reversible epimerization and deuteration at the chiral N center were detd in aqueous solns. by HPLC and NMR, resp. Results are compared with those of [Co(ox)2(Me-en)]- (H2ox = oxalic acid) and [Co(acac)2(Me-en)]+ (Hacac = acetylacetone). Factors influencing the reactions and their mechanisms are discussed.

Key words: REACTION MECHANISM, REACTION KINETICS, HIGH SPEED LIQUID CHROMATOGRAPHY, ION EXCHANGING, NMR SPECTROMETRY, TERNARY COMPLEX, ENANTIOMORPH, COBALT COMPLEX, PERCHLORATE, REACTION RATE

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