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化学学报
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化学学报 ›› 2000, Vol. 58 ›› Issue (10): 1270-1274. 上一篇    下一篇

研究论文

铜与苯并-1,3-噻唑-2-硫酮配合物的电化学合成与 晶体结构

顾建胜;马美华;沈理明;郁开北   

  1. 苏州大学理学院化学化工系;中国科学院成都分院
  • 发布日期:2000-10-15

Electrochemical synthesis and crystal structure of copper(Ⅰ) complex with benzo-1,3-thiozoline-2-thione

Gu Jiansheng;Ma Meihua;Shen Liming;Yu Kaibei   

  • Published:2000-10-15

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454

被引次数

16 | 1

在苯并-1,3-噻唑-2-硫酮(Hbztzt,HL)和三苯膦(PPh~3)的乙腈溶液中，用牺牲铜阳极的电化学方法一步合成了Cu(Ⅰ)的相应配合物，电化学效率(E~f)、元素分析和IR光谱表明：产物为同时含有硫醇阴离子(L)和中性硫酮(HL)两种配体及三苯膦的多元混合配体配合物[Cu(L)(HL)(PPh~3)]。配合物在CS~2中重结晶得淡黄色晶体，X射线单晶衍射法测定其结构为[Cu(L)(HL)(PPh~3)~2]·CS~2。晶体属三斜晶系，空间群：P1.a=1.0159(2)nm，b=1.4200(2)nm，c=1.8072(3)nm，α=78.12(1)°,β=86.56(1)°，γ=67.65(1)°，Z=2，V=2.3929(6)nm^3，D~c=1.41g·cm^-^3，R=0.0348，R~w=0.0316。Cu原子以变形四面体与两个PPh~3的两个P原子、被氢键(N－H…N)平均化的硫醇阴离子(L)和中性硫酮分子(HL)上的两个环外S原子配位(两个Cu－S键的键长为0.2372nm和0.2410nm)。

关键词: 铜络合物, 苯并噻唑P, 硫酮, 晶体结构, 元素分析, 红外分光光度法, 电化学合成

Complex [Cu(bztzt)(Hbztzt)(PPh~3)] was synthesized by electrochemical oxidation of copper in an acetonitrile solution of benzo-1,3-thiozoline-2-thione (Hbztzt) and triphenylphosphine (PPh~3), and characterized by elemental analysis and IR spectrum. The complex was dissolved in CS~2, from which yellow crystal formed. The structure of the crystal was shown to be [Cu(bztzt)(Hbztzt)(PPh~3)]· CS~2 by an X-ray structure determination. Crystal is triclinic, space group P1, with a=1.0159(2) nm, b=1.4200(2) nm, c=1.8072(3) nm, α=78. 12(1)°,β=86.56(1)°, γ=67.65(1)°, Z=2. The structure was refined to R=0.0348 and R~w=0.0316 for 4869 reflections. The copper atom is pseudotetrahedrally coordinated by two P atoms from PPh~3 and two exocyclic S atoms from bztzt^- and Hbztzt ligands respectively. The ligands of bztzt^- and Hbztzt were "averaged" by the presence of hydrogen bond (N－H…N) between them. The bond distances of two Cu－ S are 0.2372nm and 0.2410nm.

Key words: COPPER COMPLEX, BENZOTHIAZOLE P, THIOKETONE, CRYSTAL STRUCTURE, ELEMENTAL ANALYSIS, INFRARED SPECTROPHOTOMETRY, ELECTROCHEMICAL SYNTHESIS

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