An Unsymmetrical, Cyclic Diborene Based on a Chelating CAAC Ligand and its Small-Molecule Activation and Rearrangement Chemistry
2021
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 B2Br4(SMe2)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- AuI π complexes, while reaction with DurBH2, P4 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 boraketene, which readily coordinated to Ag I via its B=C double bond.
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