A Three‐Dimensional Inorganic Analogue of 9, 10‐Diazido‐9, 10‐Diboraanthracene: A Lewis Superacidic Azido Borane with Reactivity and Stability. (29th July 2022)

• Record Type: Journal Article
• Authors: Zhang, Chonghe; Liu, Xiaocui; Wang, Junyi; Ye, Qing
• Is Part Of: Angewandte Chemie. Volume 134:Number 36(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-07-29
• Subjects: Azido Borane -- Boracycle -- E−H Bond Activation -- Lewis Superacid -- Structure Elucidation; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202205506
• Languages: English
• ISSNs: 0044-8249

Abstract

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 (Et3 SiH, PhMe2 SiH) 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. Abstract : The 3D analogue of 9, 10‐diazido‐9, 10‐dihydrodiboraanthracene exists as a monomer in both the solid and solution state. It is thermally stable up to 230 °C, representing a rare example of an azido borane with boosted Lewis acidity and stability in one. Apart from the classical acid‐base and Staudinger reactions, it is capable of E−H bond activation (E=B, Si, Ge).