From Bidentate Gallium Lewis Acids to Supramolecular Complexes
From Bidentate Gallium Lewis Acids to Supramolecular Complexes
复制标题
DOI：
10.1002/anie.201701303
复制
发表时间：
2017-05-22
影响因子：
16.6
通讯作者：
Mitzel, Norbert W.
中科院分区：
文献类型：
--
作者：
Horstmann, Jan;Hyseni, Mentor;Mitzel, Norbert W.
用二乙炔基二苯基硅烷与纯三甲基或三乙基镓反应，合成了双齿镓刘易斯酸。双[（二甲基没食子基）乙炔基]二苯基硅烷（1）和二乙基没食子基衍生物2通过NMR光谱表征为Et 2 O或吡啶加合物;分离出2.2Py。刘易斯酸1和2与二齿氮碱形成主体-客体加合物，但限定的环状1：1加合物仅在1与具有匹配的N中心点中心点N距离的碱之间形成：4，4 '-二甲基-3，3'-联吡啶基乙炔（3）、双[（吡啶-3-基）乙炔基]二苯基硅烷（4）和双[（2-甲基吡啶-5-基）乙炔基]二苯基硅烷（5）。通过X射线衍射实验确定了加合物1.3、1.4和1.5的结构。2.2Py与DABCO反应得到聚合物（DABCO-2-）（n）。
Bidentate gallium Lewis acids were prepared by the reaction of diethynyldiphenylsilane with neat trimethyl-or triethylgallium. Bis[(dimethylgallyl)ethynyl]diphenylsilane (1) and diethylgallyl derivative 2 were characterized as Et2O or pyridine adducts by NMR spectroscopy; 2.2Py was isolated. Lewis acids 1 and 2 form host-guest adducts with bidentate nitrogen bases, but defined cyclic 1: 1 adducts are only formed between 1 and bases with matching N center dot center dot center dot N distances: 4,4'-dimethyl-3,3'-bipyridinylacetylene (3), bis[(pyridin-3-yl)ethynyl]diphenylsilane (4), and bis[(2-methylpyridin-5-yl)ethynyl]diphenylsilane (5). The structures of adducts 1.3, 1.4, and 1.5 were established by X-ray diffraction experiments. 2.2Py reacts with DABCO to afford polymeric (DABCO-2-)(n).