Ambiphilic boron in 1,4,2,5-diazadiborinine

Boranes have long been known as the archetypal Lewis acids owing to an empty p-orbital on the boron centre. Meanwhile, Lewis basic tricoordinate boranes have been developed in recent years. Here we report the synthesis of an annulated 1,4,2,5-diazadiborinine derivative featuring boron atoms that exhibit both Lewis acidic and basic properties. Experimental and computational studies confirmed that two boron atoms in this molecule are spectroscopically equivalent. Nevertheless, this molecule cleaves C–O, B–H, Si–H and P–H bonds heterolytically, and readily undergoes [4+2] cycloaddition reaction with non-activated unsaturated bonds such as C=O, C=C, C≡C and C≡N bonds. The result, thus, indicates that the indistinguishable boron atoms in 1,4,2,5-diazadiborinine act as both nucleophilic and electrophilic centres, demonstrating ambiphilic nature.