title: Halobenzenes and Ir(I): kinetic C-H oxidative addition and thermodynamic C-Hal oxidative addition.
abstract: A (PNP)Ir fragment undergoes facile, room-temperature oxidative addition of C-H bonds in arenes and haloarenes in preference to aromatic carbon-halogen bonds. This preference, however, is determined to be kinetic in nature. Oxidative addition of C-Cl and C-Br is preferred thermodynamically. The products of the C-Cl or C-Br oxidative addition are separated from the C-H oxidative addition products by a high activation barrier and are only accessible at >100 degrees C. Of the C-H oxidative addition products of chlorobenzene, the isomer with the o-ClC6H4 ligand has the lowest energy.
authors.affiliation: Department of Chemistry, Brandeis University, Waltham, Massachusetts 02454, USA.
authors.forename: Lei
authors.initials: L
authors.lastname: Fan
authors.forename: Sean
authors.initials: S
authors.lastname: Parkin
authors.forename: Oleg V
authors.initials: OV
authors.lastname: Ozerov