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高等学校化学研究 ›› 1993, Vol. 9 ›› Issue (4): 282-287.

• Articles • 上一篇    下一篇

Studies on Electrophilic Substitution of Quasi-Aromatic Metal Ion Complexes

XIA Xiao-ping1, HE Hai-ying1, LI Ming1, ZHAO Cheng-xue2   

  1. 1. Department of Chemistry, Huazhong University of Science and Technology, Wuhan, 430074;
    2. National Laborotory of Applied Organic Chemistry, Lanzhou University, Lanzhou, 730000
  • 收稿日期:1993-03-15 出版日期:1993-12-24 发布日期:2011-08-17
  • 基金资助:

    Supported by the National Natural Science Foundation of China

Studies on Electrophilic Substitution of Quasi-Aromatic Metal Ion Complexes

XIA Xiao-ping1, HE Hai-ying1, LI Ming1, ZHAO Cheng-xue2   

  1. 1. Department of Chemistry, Huazhong University of Science and Technology, Wuhan, 430074;
    2. National Laborotory of Applied Organic Chemistry, Lanzhou University, Lanzhou, 730000
  • Received:1993-03-15 Online:1993-12-24 Published:2011-08-17
  • Supported by:

    Supported by the National Natural Science Foundation of China

PDF (PC)

摘要： The electrophilic substitution reaction occurring to the chelate ring of the complexes could be regarded as an indication of quasi-aromaticity of the ring systems, no catalyst was used and only triethylamine was employed, implying that the aroylating agents with different p-substituents are polarized enough to be effective electrophiles to attack the methine carbon of the electron-rich substrate 1. This property is probably the clue to polarization of the ligand electrons by the nickel(Ⅱ) ion and to the participation of the nickel(Ⅱ) in the π-bond systems of the two coordinated conjugated rings. The linearity relationship between vd-d maxima, E1/2OX(1) and σp are obtained, respectively. The electronic environment of central metal ion as well as the aromaticity of the ring system are affected by the electronic properties of the p-substituents. A comparison of the electrochemical results with each other showed .that when the electronegativity of the substituent was higher, the oxidation(Ni2+/Ni3+) becomes more difficult.

关键词: Electrophilic substitution, Quasi-aromatic metal ions, Complex

Abstract: The electrophilic substitution reaction occurring to the chelate ring of the complexes could be regarded as an indication of quasi-aromaticity of the ring systems, no catalyst was used and only triethylamine was employed, implying that the aroylating agents with different p-substituents are polarized enough to be effective electrophiles to attack the methine carbon of the electron-rich substrate 1. This property is probably the clue to polarization of the ligand electrons by the nickel(Ⅱ) ion and to the participation of the nickel(Ⅱ) in the π-bond systems of the two coordinated conjugated rings. The linearity relationship between vd-d maxima, E1/2OX(1) and σp are obtained, respectively. The electronic environment of central metal ion as well as the aromaticity of the ring system are affected by the electronic properties of the p-substituents. A comparison of the electrochemical results with each other showed .that when the electronegativity of the substituent was higher, the oxidation(Ni2+/Ni3+) becomes more difficult.

Key words: Electrophilic substitution, Quasi-aromatic metal ions, Complex