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

Abstract

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 Nα upon N2 elimination, the Si−H (Et3SiH, PhMe2SiH) activation proceeded stepwise via 1,2‐addition, with the key intermediates 5int and 6int being isolated and characterized. In contrast, the cooperative Ge−H was reversible and stayed at the 1,2‐addition step.