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

Chonghe Zhang, Xiaocui Liu, Junyi Wang, Qing Ye

2022Angewandte Chemie International Edition35 citationsDOIOpen Access PDF

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 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.

Topics & Concepts

BoraneChemistryLewis acids and basesReactivity (psychology)NonaneMonomerMedicinal chemistrySolid-stateStereochemistryPolymer chemistryOrganic chemistryPhysical chemistryCatalysisPolymerAlternative medicineMedicinePathologyOrganoboron and organosilicon chemistryBoron Compounds in ChemistryCrystallography and molecular interactions
A Three‐Dimensional Inorganic Analogue of 9,10‐Diazido‐9,10‐Diboraanthracene: A Lewis Superacidic Azido Borane with Reactivity and Stability | Litcius