title: Carbon-hydrogen vs. carbon-halogen oxidative addition of chlorobenzene by a neutral iridium complex explored by DFT.
abstract: Density functional theory (DFT) is used to explore the competitive C-H and C-Cl oxidative additions (OA) of chlorobenzene to the neutral Ir(i) complex: (PNP)Ir(I) [PNP = bis(Z-2-(dimethylphosphino)vinyl)amino]. Consistent with experimental results, our calculation shows that C-H OA is kinetically favored with an activation free-energy barrier of DeltaG(double dagger) = 17.2 kcal mol(-1) that is significantly lower than that for the C-Cl activation at DeltaG(double dagger) = 24.2 kcal mol(-1). However, C-Cl OA is thermodynamically preferred and the C-Cl OA product is 22.6 kcal mol(-1) more stable than the most stable C-H OA product. The calculations also show that the lowest energy path for the conversion of the C-H OA product to the more stable C-Cl OA product is intramolecular through a "benzyne"-type intermediate.
authors.affiliation: Department of Chemistry, Texas A & M University, College Station, Texas 77843-3255, USA.
authors.forename: Hong
authors.initials: H
authors.lastname: Wu
authors.forename: Michael B
authors.initials: MB
authors.lastname: Hall