大空间位阻的2,9-双噻吩-1,10-菲咯啉-5,6-二酮铜(Ⅱ)配合物 |
A Cu(Ⅱ) Complex with2,9-Dithienyl-1,10-phenanthroline-5,6-dione Ligand with Large Steric Hindrance |
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摘要: 基于1,10-菲咯啉-5,6-二酮2,9位双噻吩的扩展策略,设计合成了2个化合物1和2.有趣的是,在大位阻双齿螯合配体2的配位化学研究中发现,只有铜(Ⅱ)离子生成了稳定的配合物3·H2O.此外,对2,2·CHCl3和3·H2O的X-射线单晶结构研究表明,为了克服空间位阻以满足中心铜(Ⅱ)离子的配位构型要求,1,10-菲咯啉-5,6-二酮及其2,9位取代的2个噻吩环之间的二面角分别从自由配体中的1.9(2)°、5.2(6)°和25.3(3)°、34.9(3)°增加到了铜(Ⅱ)配合物中的5.6(2)°、6.5(6)°和27.2(3)°、38.2(3)°. |
关键词: 铜(Ⅱ))配合物 1,10-菲咯啉-5,6-二酮 噻吩衍生物 偶联反应 |
基金项目: 国家自然科学基金(No.21171088);"青蓝工程"资助项目 |
Abstract: 1,10-Phenanthroline-5,6-dione based molecules (1 and 2), extended by two thiophene rings at 2 and 9 positions, have been designed and prepared successfully. It is interesting to mention that the study of coordination chemistry of this large steric ligand 2 with some transition-metal ions reveals that only a Cu(Ⅱ) complex 3·H2Ocan be yielded. The conformation of ligand 2 undergoes great alteration after Cu(Ⅱ) ion complexation, where the dihedral angles between the central 1,10-phenanthroline-5,6-dione and its neighboring two thiophene rings are significantly increased from 1.9(2)°/5.6(2)° in 2 and 5.2(6)°/6.5(6)° in 2·CHCl3 to 25.3(3)°/27.2(3)° and 34.9(3)°/38.2(3)° in 3·H2O in order to meet the geometric requirement of four-coordinate Cu(Ⅱ) centre. CCDC: 1013452, 2; 1013453, 2·CHCl3; 1013454, 3·H2O. |
Keywords: copper(Ⅱ) complex 1,10-phenanthroline-5,6-dione thiophene derivative coupling reaction |
投稿时间:2014-09-07 修订日期:2014-10-07 |
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金超,王银歌,钱惠芬,黄伟.大空间位阻的2,9-双噻吩-1,10-菲咯啉-5,6-二酮铜(Ⅱ)配合物[J].无机化学学报,2015,31(2):413-419. |
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