Consecutive Aromatic Carbon–Fluorine Bond and Carbon–Hydrogen Bond Activations by Iridium Porphyrins

Consecutive aromatic C–F bond and C–H bond activations of aryl fluorides were achieved by iridium porphyrins to initially give aryl and finally fluoroaryl iridium porphyrins. The C–F bond activation product is generated first, which is the precursor for the C–H bond activation. Both experimental and theoretical results support that the C–F bond is cleaved by iridium porphyrin anion through nucleophilic aromatic substitution, and the C–H bond cleavage is through homolytic aromatic substitution by iridium porphyrin radical followed by hydrogen atom abstraction. Moreover, the meta-fluorophenyl iridium porphyrin is the most thermodynamic stable regioisomers.