有机化学 ›› 2017, Vol. 37 ›› Issue (5): 1300-1305.DOI: 10.6023/cjoc201611035 上一篇    下一篇

研究简报

两种β-二亚胺锡化合物的合成与表征(英文)

马小莉, 邓紫嫣, 姚苗苗, 钟明东, 李文玲, 杨智   

  1. 北京理工大学化学与化工学院 北京 100081
  • 收稿日期:2016-11-25 修回日期:2016-12-30 发布日期:2017-02-08
  • 通讯作者: 马小莉,杨智 E-mail:maxiaoli@bit.edu.cn;zhiyang@bit.edu.cn
  • 基金资助:

    国家自然科学基金(No.21671018)资助项目.

Synthesis and Characterization of Two β-Diketiminato Tin(Ⅳ) Compounds

Ma Xiaoli, Deng Ziyan, Yao Miaomiao, Zhong Mingdong, Li Wenling, Yang Zhi   

  1. School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081
  • Received:2016-11-25 Revised:2016-12-30 Published:2017-02-08
  • Contact: 10.6023/cjoc201611035 E-mail:maxiaoli@bit.edu.cn;zhiyang@bit.edu.cn
  • Supported by:

    Project supported by the National Nature Science Foundation of China (No. 21671018).

NN-二(2,6-二异丙基苯基)-2,4-戊二亚胺的锂盐与二甲基二氯化锡的反应以及NN-二(2,6-二乙基苯基)-2,4-戊二亚胺的锂盐与三甲基氯化锡的反应均以物质的量比为1:1在室温下进行,分别得到了新化合物N(Ar)=C(Me)CH=C(NHAr)CH2SnMe2Cl·C7H81)(Ar=2,6-iPr2C6H3)和[N(Ar')C(Me)=CHC(=NAr')CH2SnMe2]2·CH2Cl22)(Ar'=2,6-Et2C6H3).通常来说,β-二亚胺配体与金属卤化物反应容易形成氮-金属-氮键,而化合物12中由于SnMe2Cl与SnMe3基团的路易斯酸性使得锡-氮键断裂和锡-碳键的生成得到了少见的氮-锡-碳键.化合物2是罕见的具备两个共振结构式的锡二聚体.通过核磁共振、元素分析及X射线单晶衍射分析鉴定了这两种化合物的结构.通过这两个结构的对比探讨了二聚体2的形成机理.

关键词: β-二亚胺配体, 金属卤化物, 锡二聚体, 氮-锡-碳键

The reactions of L1Li [L1=HC(CMeNAr)2, Ar=2,6-iPr2C6H3] with Me2SnCl2, and L2Li [L2=HC(CMeNAr')2, Ar'=2,6-Et2C6H3] with Me3SnCl in a molar ratio of 1:1 were carried out at room temperature and acquired two new compounds, N(Ar)=C(Me)CH=C(NHAr)CH2SnMe2Cl·C7H8 (1) and [N(Ar')C(Me)=CHC(=NAr')CH2SnMe2]2·CH2Cl2 (2), respectively. Different from regular nitrogen-metal-nitrogen bonds generated by the reactions of β-diketiminato ligands with metal halides, uncommon nitrogen-tin-carbon bonds in compounds 1 and 2 were obtained by Sn-N bond cleavage and concomitant Sn-C bond formation due to the Lewis acidity of SnMe3 and SnMe2Cl group. Compound 2 is a rare tin dimer with two resonant structures. Two compounds have been confirmed by 1H NMR, 13C NMR, elemental analysis, and single crystal X-ray structural analysis. Through the comparison of compounds 1 and 2, the formation mechanism of dimer 2 has been investigated.

Key words: β-diketiminato ligands, metal halides, tin dimer, nitrogen-tin-carbon bonds