Tobias Brückner, Rian D. Dewhurst, Theresa Dellermann, Marcel Müller, Holger Braunschweig

• A set of diboryldiborenes are prepared by the mild, catalyst-free, room-temperature diboration of the B–B triple bonds of doubly base-stabilized diborynes. Two of the product diboryldiborenes are found to be air- and water-stable in the solid state, an effect that is attributed to their high crystallinity and extreme insolubility in a wide range of solvents.