高等学校化学学报

高等学校化学学报 ›› 2002, Vol. 23 ›› Issue (10): 1842.

• 研究论文 • 上一篇    下一篇

四氮杂-18-冠-6的锌/铜(Ⅱ)配合物的合成与结构

郭雪雁1, 朱文祥1, 延玺1, 王如骥2, 李勇2   

  1. 1. 北京师范大学化学系, 北京 100875;
    2. 清华大学化学系, 北京 100084
  • 收稿日期:2001-11-14 出版日期:2002-10-24 发布日期:2002-10-24
  • 通讯作者: 朱文祥(1941年出生),男,教授,博士生导师,从事大环配位化学研究.
  • 基金资助:

    国家自然科学基金(批准号:29771005)资助

Syntheses and Crystal Structures of Complexes Zinc and Copper(Ⅱ) Nitrates with 1,10-Dioxa-4,7,13,16-tetraazacyclooctadecane

GUO Xue-Yan1, ZHU Wen-Xiang1, YAN Xi1, WANG Ru-Ji2, LI Yong2   

  1. 1. Department of Chemistry, Beijing Normal University, Beijing 100875, China;
    2. Department of Chemistry, Tsinghua University, Beijing 100084, China
  • Received:2001-11-14 Online:2002-10-24 Published:2002-10-24

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被引次数

7

摘要： 合成了1,10-二氧-4,7,13,16-四氮杂-18-C-6(以下用L代表)的硝酸锌和硝酸铜(Ⅱ)配合物.配合物Cu(L)(NO3)2晶体属正交晶系,Pbca空间群,晶胞参数如下:a=1.5744(6)nm,b=1.2676(4)nm,c=1.8983(6)nm,V=3.789(2)nm3,Z=8,最终偏离因子R1=0.0431,wR2=0.0904.配合物Zn(L)(NO3)2晶体属正交晶系,Pnna空间群,晶胞参数a=1.61356(10)nm,b=1.32871(11)nm,c=0.86260(5)nm,V=1.8494(2)nm3,Z=4,最终偏离因子R1=0.0718,wR2=0.1950.冠醚环上的4个氮原子和2个氧原子都参与了配位,NO3-未参与配位,中心金属离子的配位数为6.红外光谱、1H NMR和EPR谱等研究佐证了上述测定结果.Cu(L)(NO3)2循环伏安实验表明该配合物在-1.0～0V电压范围内,只发生Cu(Ⅱ)→Cu(Ⅰ)的还原反应,而在-1.6～0V电压范围内,发生Cu(Ⅰ)→Cu(0)的反应.

关键词: 二氧-四氮杂冠醚, 锌/铜配合物, 晶体结构

Abstract: Two new complexes zinc and copper (Ⅱ) nitrates with 1,10-dioxa-4,7,13,16-tetraazacyclooctadecane (L) were synthesized. Cu(L)(NO3)2 crystalizes in orthorhombic, space group Pbca, a=1.574 4(6) nm, b=1.267 6(4) nm, c=1.898 3(6) nm, Z=8, V=3.789(2) nm3; Zn(L)(NO3)2 crystalizes in orthorhombic system, space group Pnna, a=1.613 56(10) nm, b=1.328 71(11) nm, c=0.862 60(5) nm, Z=4, V=1.849 4(2) nm3. Structure refinement converged to R1=0.043 1, wR2=0.090 4 for Cu(L)(NO3)2 and R1=0.071 8, wR2=0.195 0 for Zn(L)(NO3)2, respectively. Copper(Ⅱ) and zinc ions are coordinated to four nitrogen and two oxygen atoms from the azacrown ether moiety, but not to the nitrate anions. The coordination numbers for both copper(Ⅱ) and zinc ions are six. These complexes have also been characterized by IR, 1H NMR and EPR spectroscopies. The cyclic voltammogram shows that Cu(L)(NO3)2 undergoes a reversible reduction, Cu(Ⅱ)→Cu(Ⅰ) in acetonitrile in the range of -1.0～0 V, E 1/2=-0.56 V and an irreversible reduction, Cu(Ⅰ)→Cu(0) in the range of -1.6～0 V, E1/2=-1.20 V.

Key words: Dioxa-tetraazacrown ether, Zinc and copper(Ⅱ) complexes, Crystal structure

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