波谱学杂志 ›› 2010, Vol. 27 ›› Issue (4): 524-531.

• 恭贺沈联芳和杜有如两位先生八十华诞专栏 • 上一篇    下一篇

(C5H11N2)+和(C7H12N2)2+的NMR研究

喻冲1,李志强1,2, 毕研刚1,史旭东1,朱琳丽1,夏寺丰1,鲁晓明1,2*   

  1. 1. 首都师范大学 化学系,北京 100048;2. 中国科学院 武汉物理与数学研究所,湖北 武汉 430071
  • 收稿日期:2010-04-29 修回日期:2010-06-27 出版日期:2010-12-05 发布日期:2010-12-05
  • 基金资助:

    国家自然科学基金资助项目(20871085), 北京市自然科学基金资助项目(2092009).

An NMR Studies of (C5H11N2)+ and (C7H12N2)2+

YU Chong1, LI Zhi-qiang1,2, BI Yan-gang1, SHI Xu-dong1, ZHU Lin-li1, Xia Si-feng1, LU Xiao-ming1,2*   

  1. 1. Department of Chemistry, Capital Normal University, Beijing 100048, China;
    2. Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, China
  • Received:2010-04-29 Revised:2010-06-27 Online:2010-12-05 Published:2010-12-05
  • Supported by:

    国家自然科学基金资助项目(20871085), 北京市自然科学基金资助项目(2092009).

摘要:

结合1H NMR,13C NMR谱,分别对钨、钼配合物{WO2(C10H6O2)2(C5H11N2)2[H2N(CH2)3NH2]}3 (1),{(C5H11N2)2[H2N(CH2)3NH2][MoO2(C10H6O2)2]} (2),{(C7 H12N2)2[MoO2(C10H8O2)2]} (3)晶体结构中小分子环进行了归属. 其中,配合物12中(C5H11N2)+的NMR研究证实了六元环由1, 3-丙二胺和乙腈化合而成,配合物3中(C7H12N2)2+的NMR谱图证实了七元环由乙二胺和乙酰丙酮化合而成,并且推导出这些亲核加成-消除反应的反应机理. 配合物1~3中的小分子环的合成在其它体系中尚未见报导,而在合成它们的反应中作为新产物随主体晶体析出,并由晶体结构解析和NMR得到了证实.

关键词: 核磁共振(NMR), 归属, (C5H11N2)+, (C7H12N2)2+, 亲核加成-消除反应

Abstract:

The structure of small molecular rings (C5H11N2)+ and (C7H12N2)2+ in tungstate and molybdate complexes {WO2(C10H6O2)2(C5H11N2)2[H2N(CH2)3NH2]}3  (1),  {(C5H11N2)2[H2N(CH2)3NH2][MoO2(C10H6O2)2]} (2) and {(C7H12N2)2[MoO2(C10H8O2)2]} (3) were studied by 1H and 13C NMR. The NMR data of (C5H11N2)+ in complexes 1 and 2 indicated  the existence of two six-membered rings, which are composed of 1,3-diaminopropane and acetonitrile. The NMR spectra of (C7H12N2)2+ in complex 3 indicated the existence of a seven-membered ring, which is composed of ethylenediamine and acetylacetone, inferring a formation mechanism of nucleophilic additionelimination reactions. The synthesis of small molecular rings in complexes 1~3 have not been reported in other systems. In our works, these ring structures precipitated with the host-frames as new products in complexes 1~3, as confirmed by crystal structure analysis and NMR data.

Key words: NMR, chemical shift assignment, (C5H11N2)+, (C7H12N2)2+, nucleophilic addition-elimination reaction

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