Acta Chimica Sinica ›› 1983, Vol. 41 ›› Issue (7): 623-629. Previous Articles     Next Articles

Original Articles

某些芳香族羟肟一过渡金属配合物的红外光谱

周澄明;陈星;袁承业   

  1. 中国科学院上海有机化学研究所
  • 发布日期:1983-07-15

Investigation of aromatic hydroxyoxime-transition metal complexes by infrared spectroscopy

ZHOU CHENGMING;CHEN XING;YUAN CHENGYE   

  • Published:1983-07-15

The preparation and infrared spectroscopic studies of coordination compounds of salicylaldoxime, 2-hydroxy-acetophenone oxime, 2-hydroxy-benzophenone oxime and 2-hydroxy-4-methoxy-benzophenone oxime with copper (II), nickel (II), cobalt (II) and iron (II) have been described. The frquency of the C=N stretching vibration is usually higher in the complex than that in the ligand. The higher the frequency of the C=N vibration is, the larger the stability constant of the complex will be, but there is no quantitative relationship. In the case of complexes of salicylaldoxime with Cu, Ni, Co and Fe, &CC=N values are correlated linearly with the ionization potentials of the central metal ions. The frequency of the OH stretching vibration is closely related to the geometric configuration of the complex. Thus aromatic hydroxyoximes form coordination compound with Co (II) and Fe (II) with cis configuration possessing six membered stronger hydrogen bonding ring. This is indicated in the infrared spectra by the complete absence of the absorption band due to the OH stretching vibration, or by the appearance of an extremely broad and flat band of very low intensity. However, Cu (II) or Ni (II) complex possesses trans configuration with five membered hydrogen-bonding bridge showing characteristic OH absorption band in the infrared region. The &COH of complex investigated is closely related to the polar nature of the substituents on the benzene ring. By examining the spectra of Cu-63 and Cu-65 complexes with 2-hydroxy-4(5)-substituted benzophenone oximes, the characteristic frequencies of M -- O and M -- N in the far infrared region were assigned for a series of aromatic hydroxyoxime-transition metal complexes.

Key words: INFRARED SPECTROPHOTOMETRY, IRON COMPLEX, DIPHENYLMETHANONE P, COPPER COMPLEX, ACETOPHENONE P, OXIME, COBALT COMPLEX, TRANSITION METAL COMPLEX, NICKEL COMPLEX, CONFIGURATION

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