Halobenzenes and Ir(I):  Kinetic C−H Oxidative Addition and Thermodynamic C−Hal Oxidative Addition

摘要: A (PNP)Ir fragment undergoes facile, room-temperature oxidative addition of C−H bonds in arenes and haloarenes preference to aromatic carbon−halogen bonds. This preference, however, is determined be kinetic nature. Oxidative C−Cl C−Br preferred thermodynamically. The products the or are separated from by a high activation barrier only accessible at >100 °C. Of chlorobenzene, isomer with o-ClC6H4 ligand has lowest energy.