Access to Unsupported Iminobismuthane and Tetraazabismole Species Enabled by a Rigid and Bulky Organobismuthinidene

Herein, we report the reactivity of a monocoordinate bismuthinidene ( 1 ) with various organic azides. The reaction of 1 with p ‐toluenesulfonyl azide resulted in the formation of an unprecedented, unsupported iminobismuthane ( 2 ), which features the shortest reported Bi–N distance of 2.041(3) Å in an iminobismuthane. Conversely, the reaction of 1 with 4‐azidobiphenyl resulted in the first example of a species containing a tetraazabismole (BiN 4 ) heterocycle ( 3 ). We also highlight that 1 demonstrates catalytic activity, enabling the reduction of a selection of organic azides.