Dewar benzene, one of the isolable valence isomers of CH, has been extensively studied since its first synthesis in 1962. By contrast, the chemistry of inorganic congeners of Dewar benzene, which can be formally gained by replacing the skeletal carbon atoms with heteroatoms, has been less developed despite their peculiar structural and electronic features. Among them, the extant B,N-Dewar benzenes are limited to the BN system. Herein, we report the development of the first example of an isolable BN Dewar benzene, . As predicted by DFT calculations, a judicious selection of the substituents allows synthesizing . Single-crystal X-ray analysis, NMR, and computational studies confirmed that possesses a high-lying B(sp)-B(sp) σ-bond at the bridgehead position. Reactions with ethylene and phenylacetylene proceeded smoothly under mild conditions, affording the fused BCN ring systems ( and ). Structural characterization as well as DFT calculations revealed that compounds and involve a rigid and conjugated (BN) tetraene scaffold. Formation of and demonstrates that may serve as a building block for the construction of conjugated B,N-chains.
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