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.