Unexpected Synthesis of a Perfluoroacyl Complex, Cp*Ir(CO)(COC6F11)Br, by Direct Fluoroalkylation of a CO Ligand, and Elimination of Perfluorocyclohexene by Activation of a γ-C−F Bond

Instead of oxidative addition at iridium to form a perfluorocyclohexyl iridium complex, reaction of C6F11Br with Cp*Ir(CO)2 at −78 °C gave a perfluoroacyl complex Cp*Ir(CO)(COC6F11)(Br) by direct fluoroalkylation at a CO ligand. Reduction of the perfluoroacyl complex with KC8 afforded Cp*Ir(CO)2 and perfluorocyclohexene with γ-C−F bond activation.