Zhang Chonghe, Liu Xiaocui, Wang Junyi, Ye Qing
Department of Chemistry, Southern University of Science and Technology, 518055, Shenzhen, P. R. China.
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, Hong Kong.
Angew Chem Int Ed Engl. 2022 Sep 5;61(36):e202205506. doi: 10.1002/anie.202205506. Epub 2022 Jul 29.
Herein, we report the facile synthesis of a three-dimensional (3D) inorganic analogue of 9,10-diazido-9,10-dihydrodiboraantracene, which turned out to be a monomer in both the solid and solution state, and thermally stable up to 230 °C, representing a rare example of azido borane with boosted Lewis acidity and stability in one. Apart from the classical acid-base and Staudinger reactions, E-H bond activation (E=B, Si, Ge) was investigated. While the reaction with B-H (9-borabicyclo[3.3.1]nonane) led directly to the 1,1-addition on N upon N elimination, the Si-H (Et SiH, PhMe SiH) activation proceeded stepwise via 1,2-addition, with the key intermediates 5 and 6 being isolated and characterized. In contrast, the cooperative Ge-H was reversible and stayed at the 1,2-addition step.
在此，我们报道了一种9,10-二叠氮基-9,10-二氢二硼蒽的三维（3D）无机类似物的简便合成方法，结果表明该化合物在固态和溶液态均为单体，热稳定性高达230°C，是一种罕见的兼具增强路易斯酸性和稳定性的叠氮硼烷实例。除了经典的酸碱反应和施陶丁格反应外，还研究了E-H键的活化作用（E = B、Si、Ge）。与B-H（9-硼双环[3.3.1]壬烷）反应时，在消除N的同时会直接导致N上的1,1-加成反应；而Si-H（Et SiH、PhMe SiH）的活化则通过1,2-加成逐步进行，关键中间体5和6已被分离并表征。相比之下，Ge-H的协同作用是可逆的，并停留在1,2-加成步骤。
