Synthesis and Reactivity of Tricoordinate Organoberyllium Azides.

A series of terminal mono- and disubstituted beryllium azides of the form [(CAAC)Be(N 3 )R] (R=CAACH, Dur; CAACH/CAAC=1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-yl/idene, Dur=2,3,5,6-tetramethylphenyl) and [L 2 Be(N 3 ) 2 ] (L=CAACNH=1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-imine, IiPr Me =1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene), respectively, were synthesized and characterized by NMR spectroscopy and X-ray crystallography. Thermolysis and photolysis products of these first examples of tricoordinate azidoberyllium complexes evidence extensive ligand scrambling and the formal insertion of nitrenes into the CAAC-Be bond, generating cyclic alkyl(amino)imine (CAAI) ligands. Furthermore, the reaction with a small N-heterocyclic carbene (NHC) leads to unexpected CAAC-NHC ligand exchange, while the reaction with pentaphenylborole yields the first γ-azide adduct of a borole, long postulated to be the first step in the synthesis of 1,2-azaborinines from boroles and azides.