Suzuki–Miyaura cross-coupling reaction catalyzed by [R3Si–IPr]Pd complexes: a computational study

The cross-coupling reaction of chlorobenzene and phenylboronic acid, catalyzed by the [R₃Si–IPr]Pd⁰ species (generated upon activation of {[R₃Si–IPr]Pd(η³-allyl)Cl} pre-catalyst complexes) in the presence of hydroxide ion as a base, was studied in details by the quantum chemical calculations. Each step of the whole process, including pre-catalyst activation, oxidative addition, transmetalation and reductive elimination, were computationally probed to locate reaction intermediates and transition states along the reaction coordinate. Accordingly, transmetalation was found to be a limiting step of the catalytic cycle (involving oxidative addition, transmetalation and reductive elimination), whereas pre-catalyst activation was revealed as a limiting step of the whole catalytic process.