高等学校化学学报

高等学校化学学报 ›› 1998, Vol. 19 ›› Issue (5): 741.

• 论文 • 上一篇    下一篇

碳酸酐酶的化学模拟——含三(取代吡唑)硼氢根的金属配合物[η3-HB(3-Ar-5-Mepz)3]MX(M=Ni,Cu,Zn,Cd;Ar=2’-thie,Ph;X=Cl,NO3)的合成和表征

郭胜利1, 刘省明1, 殷元骐1, 郁开北2   

  1. 1. 中国科学院兰州化学物理研究所, 兰州, 730000;
    2. 中国科学院成都有机化学研究所, 成都, 610041
  • 收稿日期:1996-12-02 出版日期:1998-05-24 发布日期:1998-05-24
  • 通讯作者: 殷元骐
  • 作者简介:郭胜利,男,32岁,博士研究生.
  • 基金资助:

    国家自然科学基金

The Chemical Modeling of Carbonic Anhydrase ——Synthesis and Characterization of Tris(pyrazoly)hydroborato Metal Complexes η3-HB(3-Ar5-Mepz)3 MX (M=Ni, Cu, Zn, Cd; Ar=2'-thie, Ph; X=Cl, NO3)

GUO Sheng-Li1, LIU Sheng-Ming1, YIN Yuan-Qi1, YU Kai-Bei2   

  1. 1. Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000;
    2. Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu, 610041
  • Received:1996-12-02 Online:1998-05-24 Published:1998-05-24

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摘要： 合成了标题所示的一系列新的含三(取代吡唑)硼氢根的金属配合物,均通过元素分析、IR、1H NMR进行表征.配合物[η3-HB(3-(2'-thie)-5-Mepz)3]Zn(NO3)·1/2THF(2c)的晶体结构测定表明,硝酸根是以不对称双齿方式与Zn原子配位(Zn-O(2)键长为0.1966(4)nm,Zn-O(3)键长为0.2463(4)nm);而在镉的类似物{[η3-HB(3-Ph-5-Mepz)3]Cd(NO3)(THF)}(2e)中,NO3-则以双齿方式与Cd原子配位[Cd-O键长为0.2334(3)和0.2356(3)nm].NO3-随金属不同取不同方式配位的现象,为解释锌、镉碳酸酐酶的不同活性(与酶活性中心配位的HCO3-是NO3-的等电子体)提供了进一步的依据.配合物2c和2e均为三斜晶系,P1空间群,Z=2.2c晶胞参数:a=1.16250(10),b=1.2422(2),c=1.32590(10)nm;α=71.410(10)°,β=73.090(10)°,γ=65.660(10)°;R=0.0755.2e品胞参数:a=1.13030(10),b=1.2099(2),c=1.2607(2)nm;α=102.050(10)°,β=91.780(10)°,γ=93.620(10)°;R=0.0302.

关键词: 化学模拟, 晶体结构, 三(取代吡唑)硼氢根的金属配合物, 碳酸酐酶

Abstract: A series of tris(pyrazolyl)hydroborato metal complexes, η3-HB(3-Ar-5-Mepz)3 MX(M=Ni, Cu, Zn, Cd; Ar=2'-thie, Ph; X=Cl, NO3) had been synthesized and characterized. The determination of X-ray crystal structure shows, the complex{η3-HB(3-(2'- thie)-5-Mepz)3 }Zn(NO3)·1/2THF(2c) exhibits anisobidentate coordination of the nitrate ligand Zn—O(2) 0.196 6(4) nm, Zn—O(3) 0.246 3(4) nm, in contrast to the bidentate coordination fashion that is observed in the cadmium analogue{ η3-HB(3-Ph-5-Mepz)3 Cd(NO3)(THF)}(2e) 0.233 4(3) and 0.2356(3) nm . Cadmium substituted carbonic anhydrase(CA) is less active than zinc enzyme, among many other factors, such as the p Ka of the coordinated water, that facile access to a unidentate bicarbonate intermediate may be an important requirement for CAactivity. Both of 2c and 2e are triclinic with space group P1, Z=2. For 2c, a=1.16250(10) nm, b=1.2422(2) nm, c=1.32590(10) nm; α=71.410(10)°, β=73.090(10)°, γ=65.660(10)°; final R=0.0755. While for 2e they are: a=1.13030(10) nm, b=1.2099(2) nm, c=1.2607(2) nm; α=102.050(10)°, β=91.780(10)°, γ=93.620(10)°; final R=0.0302.

Key words: Chemical modeling, Crystal structure, Tris(pyrazolyl)hydroborato metal complex, Carbonic anhydrase

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