Rapid Aerial Oxidation of Ruthenium-Dithiocatecholate Catalysts: A Challenge to Stereoretentive Olefin Metathesis

Ruthenium dithiolene complexes, particularly the dithiocatecholates Ru(S₂C₆H₂-3,6-Cl₂)(NHC)(=CHC₆H₄-2-OⁱPr) (NHC = H₂IPr, H₂IMes), are an important class of olefin metathesis catalysts employed for the stereocontrolled assembly of C=C bonds. The poorly understood sensitivity of these catalysts results in unpredictable performance. Here they are shown to resist degradation by amine nucleophiles, in contrast with their dichloride parents; however, they are significantly more oxygen-sensitive. Even as the precatalysts, they decompose within minutes in solution under O₂, eliminating the alkylidene ligand as O=CHC₆H₄-2-OⁱPr and forming unusual, four-coordinate Ru(IV)-oxo products, Ru(O)(S₂C₆H₂-3,6-Cl₂)(NHC). Participation of the latter in O-transfer with PPh₃ suggests potential opportunities in catalytic oxidation.