高等学校化学学报

高等学校化学学报 ›› 2000, Vol. 21 ›› Issue (6): 888.

• 论文 • 上一篇    下一篇

蝎型螯合过渡金属配合物的研究(Ⅰ)──氢三(3-对甲氧基苯基吡唑-1)硼酸铜(Ⅱ)配合物的合成、表征及晶体结构

邓元, 王如骥, 李勇, 孙素琴, 丁廷桢   

  1. 清华大学化学系, 北京 100084
  • 收稿日期:1999-08-10 出版日期:2000-06-24 发布日期:2000-06-24
  • 通讯作者: 丁廷桢(1938年出生),男,教授,从事金属有机配合物研究.E-mail:dtz-dce@tsinghua.edu.cn E-mail:dtz-dce@tsinghua.edu.cn
  • 基金资助:

    国家自然科学基金(批准号:29571020)

Studies on Transition-metal Complexes Containing the Scorpionate Ligand(Ⅰ) Synthesis,Characterization and Crystal Structure of Copper(Ⅱ) Complexes with Hydrotris[3-(p-methoxyphenyl( pyrazol-1-yl) )]borate

DENG Yuan, WANG Ru- Ji, L I Yong, SUN Shu- Qin, DING Ting- Zhen   

  1. Departmentof Chemistry, Tsinghua University, Beijing 100084, China
  • Received:1999-08-10 Online:2000-06-24 Published:2000-06-24

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被引次数

2

摘要： 合成了一种蝎合配体氢三(3-对甲氧基苯基吡唑-1)硼酸钾KTpAn.室温下,等物质的量的KTpAn与Cu(O2CMe)2·H2O在THF溶液中反应得配合物[Cu(O2CMe)(HB{pzAn}3)](Ⅰ);KTpAn与等物质的量的无水CuCl2反应则得不同的产物CuCl(pzAnH)(HB{pzAn}3)(Ⅱ).对标题化合物进行了元素分析、红外光谱、顺磁共振谱和电化学研究.配合物Ⅰ和Ⅱ的苯溶液的EPR谱研究表明中心金属铜的基态电子构型为拟轴对称的{dx2-y2}1.Ⅱ的X射线衍射晶体结构分析表明,铜离子的配位环境为畸变的四方锥结构,与其配位的有配体TpAn上3个吡唑氮原子、3-对甲氧基苯基吡唑氮原子和1个氯离子,晶体属空间群P21/c.a=1.1643(2)nm,b=2.7081(5)nm,c=1.4494(3)nm,β=105.37(3)°,V=4.4066(14)nm3,Z=4,R=0.0604.分子中存在弱的分子内氢键N—H…Cl,其中Cl1…N1=0.3009nm,∠Cl1…H1B—N1=120.3°.

关键词: 多吡唑硼酸盐配体, 合成, 晶体结构, 分子内氢键

Abstract: A scorpionate ligand K[HB{pzAn}3]( pzAn=3-{p-methoxyphenyl}pyrazole) was prepared, which was reacted with one molar equivalent of Cu( O2 CMe)2 · H2 Oin THFat room temperature, yielding [Cu( O2 CMe) (HB{pzAn}3) ](Ⅰ) .But the reaction of K[HB{pzAn}3]with anhydrous Cu Cl2 afforded CuCl(pzAnH) (HB{pzAn}3) (Ⅱ) .The EPR spectra of Ⅰand Ⅱ in benzene solution exhibit a pseudoaxial symmetrical {dx2-y2}1 configuration at copper.Both Ⅰ and Ⅱ are characterized by IR, elementary analysis and CV.The crystal structure of compound Ⅱ has been determined.Crystals are monoclinic,space group P21/c with a=1 .1643( 2 ) nm,b=2 .7081 ( 5) nm,c=1 .4494( 3) nm,β= 10 5.37( 3)°,V=4.4066( 14) n m3 and Z=4,with final residuals R=0 .0604 and Rw=0 .1416.The complex shows a distorted square pyramidal copper center,and exhibits a weak intramolecular hydrogen bond,N_ H… Cl,with bond length of Cl… N 0 .300 9nm and bond angle of Cl… H _ N 12 0 .3°.

Key words: Poly( pyrazolyl) borate, Synthesis, Crystal structure, Intramolecular hydrogen bond

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