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.