Direct intramolecular carbon(sp2)-nitrogen(sp2) reductive elimination from gold(III)

The reactivity of bidentate Au-III-Cl species, [(C<^>N)AuCl2], with a bisphosphine or carbon donor ligands results in reductive elimination. Combined experimental and computational investigations lead to the first evidence of a direct intramolecular C(sp(2))-N(sp(2)) bond formation from a monomeric [(C<^>N)AuCl2] gold(iii) complex. We show that bidentate ligated Au(iii) systems bypass transmetallation to form C(sp(2))-N(sp(2)) species and NHC-Au-Cl. Mechanistic investigations of the reported transformation reveal a ligand-induced reductive elimination via a key Au-III intermediate. Kinetic studies of the reaction support a second-order rate process.