骨架不含活性质子的β-二亚胺氯代锗卡宾和氯代锡卡宾的合成

Syntheses of Chlorogermylene and Chlorostannylene Supported by a β-Diketiminato Ligand Without Active Proton at α-Position

通过碳碳偶联反应合成了一例骨架不含活性质子的新型β-二亚胺MeC（PhCNDip）2H（1）（Dip=2,6-iPr2C6H3）。化合物1的锂化产物分别与GeCl2·dioxane和SnCl2反应,得到β-二亚胺氯代锗卡宾和β-二亚胺氯代锡卡宾MeC（PhCNDip）2MCl（M=Ge,2;Sn,3）。产物1~3的结构由X射线单晶衍射与核磁共振表征。2与3的结构中,二价Ge、Sn原子与相邻原子较长的化学键说明这些重主族元素的原子轨道在其低价化合物中不杂化成键的特征。

Through a salt metathesis reaction, a new type of β-diketimine MeC（PhCNDip）2H（1） （Dip=2,6-1Pr=C6H3） without active proton at α-position was prepared. The reaction of the lithiation product of 1 with GeC12dioxane and SnCl2 afforded the β-diketiminato ehlorogermylene and chlorostannylene MeC（PhCNDip）2MCl （M=Ge, 2; Sn, 3）, respectively. The compounds 1-3 were characterized by X-ray diffraction and NMR. In the structure of compounds 2 and 3, the bonds between Sn or Ge with adjacent atoms are longer than average, indicating the hybridization of atomic orbitals for heavy main-group elements is not realized in their low-valent compounds. CCDC： 1444224, 1; 1444223, la; 1444222, 2; 1444221, 3.