An Unsymmetrical, Cyclic Diborene Based on a Chelating CAAC Ligand and its Small‐Molecule Activation and Rearrangement Chemistry

A one‐pot synthesis of a CAAC‐stabilized, unsymmetrical, cyclic diborene was achieved via consecutive two‐electron reduction steps from an adduct of CAAC and B 2 Br 4 (SMe 2 ) 2 . Theoretical studies revealed that this diborene has a considerably smaller HOMO–LUMO gap than those of reported NHC‐ and phosphine‐supported diborenes. Complexation of the diborene with [AuCl(PCy 3 )] afforded two diborene–Au I π complexes, while reaction with DurBH 2 , P 4 and a terminal acetylene led to the cleavage of B−H, P−P, and C−C π bonds, respectively. Thermal rearrangement of the diborene gave an electron‐rich cyclic alkylideneborane, which readily coordinated to Ag I via its B=C double bond.