Selective arene cleavage by direct insertion of iridium into the aromatic ring

We report an unprecedented selective cleavage of aromatic C−C bonds through the insertion of well‐defined iridium complexes into the aromatic ring of simple alkylarenes. The insertion occurs at 50–100 °C without the activation of weaker C−H and C−C bonds and gives unique metallacycles in high yields. Key to the success of this approach is metal‐induced deformation of the arene ring, which creates temporary ring strain and promotes direct and selective insertion of the metal into the otherwise inert arene ring C−C bonds