Oxidatively induced metal-carbon bond cleavage reactions in iridium dimethyl complexes: Formation of cationic pyridine and nitrosyl iridium(III) alkyl derivatives

Reaction of [Ir(Me)2Cp*(L)] complexes (Cp*=?5-C5Me5; L=PPh3, PMePh2, PMe2Ph, PMe3) with equimolar amounts of [Fe Cp2]+ in pyridine gives methane and the corresponding cationic derivatives [Ir(Me)Cp*(L) (pyridine)]+. Reaction with an excess of NOBF4 yields methane and [Ir(Me)Cp*(L)(NO)]2+ (L=PMe3, PMe2Ph, PMePh2) or [Ir(Me)2Cp*(NO)]+ and [Ir(Me)Cp*(L)2]+ (L=PPh3) via the formation of the primary oxidation products [Ir(Me)2Cp*(L)]+, which have been detected by EPR spectroscopy.