Facile direct insertion of nitrosonium ion (NO+) into a ruthenium-aryl bond

An insertion reaction of nitrosonium ion (NO⁺) into the metal-carbon bond of cyclometalated ruthenium(II) complexes is prepared with experimental evidence supporting a bimolecular direct NO⁺ insertion into the metal-carbon bond (i.e., M-R + NO⁺ → [M-N(=O)-R] ⁺) but not an intramolecular migratory insertion (i.e., R-M-(NO) + L → L-M-N(=O)R) as the reaction mechanism. Theoretical calculations suggest that the direct NO⁺ insertion into the M-C bond may be rationalized as a frontier orbital interaction between the [Ru-aryl]-dominated HOMO of the Ru(II) complexes and the LUMO of the NO⁺. © 2011 American Chemical Society.