Complex dependent regioselectivity in the nucleophilic substitution of fluorine of a coordinated tetrafluoropyridyl N-heterocycle carbene

► A coordinated tetrafluoropyridyl substituted N-heterocycle carbene undergoes nucleophilic attack. ► Nucleophilic attack on the silver(I) bromide complex occurs ortho to the ring nitrogen. ► Nucleophilic attack on the pentamethylcyclopentadienylrhodium dihalide complex occurs meta to the ring nitrogen. ► The complex determines whether the nucleophilic attack is intermolecular or intramolecular.