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


3.  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, ESIMS, and X-ray crystallography. DFT calculations were performed to provide insight into the reaction mechanism. (Chem. Eur. J. 2019, 25, 10828 –10833; DOI: 10.1002/chem.201903012)