A Three‐Dimensional Inorganic Analogue of 9,10‐Diazido‐9,10‐Diboraanthracene: A Lewis Superacidic Azido Borane with Reactivity and Stability

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(α) upon N(2) elimination, the Si−H (Et(3)SiH, PhMe(2)SiH) activation proceeded stepwise via 1,2‐addition, with the key intermediates 5(int) and 6(int) being isolated and characterized. In contrast, the cooperative Ge−H was reversible and stayed at the 1,2‐addition step.