Rudlof Jens, Aders Niklas, Lamm Jan-Hendrik, Neumann Beate, Stammler Hans-Georg, Mitzel Norbert W
Chair of Inorganic and Structural Chemistry, Center of Molecular Materials CM2, Bielefeld University, Universitätsstraße 25, D-33615, Bielefeld, Germany.
ChemistryOpen. 2021 Oct;10(10):1020-1027. doi: 10.1002/open.202100198.
Starting from 1,2-diethynylbenzene, a series of bidentate Lewis acids was prepared by means of hydrometalations, in particular hydrosilylation, hydroboration, hydroalumination and terminal metalation based on group 13 and 14 elements. In the case of terminal alkyne metalation, the Lewis-acidic gallium function was introduced using triethylgallium under alkane elimination. A total of six different Lewis acids based on a semiflexible organic scaffold were prepared, bearing -SiClMe , -SiCl Me, -SiCl , -B(C F ) , -AlBis (Bis=bis(trimethylsilyl)methyl) and -GaEt as the corresponding functional units. In all cases, the Lewis acid functionalisation was carried out twice and the products were obtained in good to excellent yields. In the case of the twofold gallium Lewis acid, a different structural motif in the form of a polymer-like chain was observed in the solid state. All new bidentate Lewis acids were characterised by multinuclear NMR spectroscopy, CHN analysis and X-ray diffraction experiments.
从1,2 - 二乙炔基苯出发，通过氢金属化反应，特别是硅氢化、硼氢化、铝氢化以及基于第13和14族元素的末端金属化反应，制备了一系列双齿路易斯酸。在末端炔烃金属化的情况下，在消除烷烃的条件下使用三乙基镓引入路易斯酸性镓官能团。总共制备了六种基于半柔性有机骨架的不同路易斯酸，它们带有 -SiClMe 、-SiCl₂Me、-SiCl₃、-B(C₆F₅)₂、-AlBis（Bis = 双（三甲基硅基）甲基）和 -GaEt作为相应的官能团。在所有情况下，路易斯酸官能团化反应进行了两次，产物的产率良好至优异。对于双镓路易斯酸，在固态下观察到了聚合物状链形式的不同结构 motif。所有新的双齿路易斯酸均通过多核核磁共振光谱、CHN分析和X射线衍射实验进行了表征。
