桥联8-氨基喹啉衍生物及其锆配合物的合成及结构

Synthesis and Structures of Symmetric Bridged 8-Aminoquinolinyl Derivatives and Their Zirconium Complexes

以8-氨基喹啉和8-氨基喹哪啶为原料,通过锂化再与二甲基二氯硅烷反应,分别得到对称的桥联配体Me2Si[NH（C9H6N）]2（1a）,Me2Si[NCH3（C9H5N）]2（1b）。1a和1b分别与2倍物质的量的正丁基锂反应,然后与ZrCl4作用得到2种配位模式不同的硅桥联取代8-氨基喹啉锆配合物Zr{Me2Si[N（C9H6N）]2}2（2）和Zr{Me2Si[NCH3（C9H5N）]2}Cl2（3）。化合物1~3通过1H NMR、13C NMR和元素分析进行表征,2和3通过X-射线单晶衍射确定其晶体结构。结果表明配合物2的中心Zr原子与8个N原子配位,属于变形十二面体结构,单晶属于三斜晶系;配合物3的中心Zr原子与4个N原子和2个Cl原子配位,属于变形八面体,单晶属于正交晶系。

Treatment of 8-aminoquinoline and 8-aminoquinadine with n-BuLi in Et2 O followed by reacting with dimethyl dichlorosilane, give symmetrical bridged quinolinyl ligands Me2Si[NH（C9H6N）]2（1a） and Me2Si[NCH3（C9H5N）]2（1b） successfully. Reaction of quinolinyl ligands 1a and 1b with n-BuLi in THF, separately, then reacting with ZrCl4 in situ afford two kinds of multidentate complexes Zr{Me2Si[N（C9H6N）]2}2（2） and Zr{Me2Si[NCH3（C9H5N）]2}Cl2（3）. All the compounds have been confirmed and characterized by1 H NMR,13 C NMR and elemental analysis. Complexes 2 and 3 were characterized by single-crystal X-ray diffraction analysis. A distorted dodecahedron of N8 atoms has been found for the zirconium（Ⅳ） center of complex 2, and the crystal of complex 2belongs to triclinic space group. Complex 3 is a distorted octahedron for the zirconium（Ⅳ） center and belongs to orthorhombic space group. CCDC： 958191, 2; 999854, 3.