Issue 30, 2009

Carbon–hydrogenvs.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)IrI [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 ΔG = 17.2 kcal mol−1 that is significantly lower than that for the C–Cl activation at ΔG = 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.

Graphical abstract: Carbon–hydrogen vs. carbon–halogen oxidative addition of chlorobenzene by a neutral iridium complex explored by DFT

Supplementary files

Article information

Article type
Paper
Submitted
03 Feb 2009
Accepted
24 Mar 2009
First published
05 May 2009

Dalton Trans., 2009, 5933-5942

Carbonhydrogen vs. carbonhalogen oxidative addition of chlorobenzene by a neutral iridium complex explored by DFT

H. Wu and M. B. Hall, Dalton Trans., 2009, 5933 DOI: 10.1039/B902176K

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