Nucleophilic Attack in Methoxycarbenes: Heterolytic Cleavage of the Carbon (sp³)–Oxygen Bond versus Aminolysis

The iridium methoxycarbene [IrCp*Cl­{C­(OMe)­CHCPh2}­(PPh2Me)]­PF6 (3) can undergo a clean attack by nucleophiles at least by two different pathways: (1) an unusual nucleophilic attack of primary, secondary, and tertiary amines at the sp3 carbon–oxygen bond, which gives an acyl complex and amine alkylation and (2) a nucleophilic attack of the ammonia at the carbenic carbon, which forms a primary aminocarbene.