Intramolecular Nitrene Insertion into Saturated C−H‐Bond‐Mediated C−N Bond Cleavage of a Coordinated NHC Ligand

Ruthenium(II) complexes bearing a tridentate bis(N‐heterocyclic carbene) ligand reacted with iminoiodanes (PhI=NR) resulting in the formation of isolable ruthenium(III)–amido intermediates, which underwent cleavage of a C−N bond of the tridentate ligand and formation of an N‐substituted imine group. The RuIII–amido intermediates have been characterized by 1H NMR, UV/Vis, ESI‐MS, and X‐ray crystallography. DFT calculations were performed to provide insight into the reaction mechanism. N ligands: C−N bond cleavage of a coordinated N‐heterocyclic carbene (NHC), following an intramolecular nitrene C(sp3)−H insertion, has been observed by reaction of PhI=NR with RuII–NHC complexes 1 bearing a tridentate bis(NHC) ligand, resulting in formation of RuII‐imine complexes 2 (see scheme).