Viable pathways for the oxidative addition of iodobenzene to palladium(0)-triphenylphosphine-carbonyl complexes: a theoretical study.

The oxidative addition of 4-substituted iodobenzenes on Pd(0) catalysts under CO atmosphere was investigated by means of density functional calculations employing the M06//B97-D3 level of theory. The 18-electron triphenylphosphine-tricarbonyl complex was found to be the global minimum. Several coordinatively unsaturated species are predicted to be present both in N,N-dimethylformamide and toluene solution. In terms of activating iodobenzene, bis(triphenylphosphine)palladium(0) was proved to be the most active. However, due to its lower thermodynamic stability, it is slightly inferior to the Pd-triphenylphosphine-carbonyl complex, which is predicted to react with a free energy of activation of 23.2 kcal mol-1 with respect to the initial resting state tetrakis(triphenylphosphine)palladium(0). The effect of 4-substituents of iodobenzene on reaction energetics is also discussed. The activity of the Pd(0) catalyst was found to be governed by the donor-acceptor strength of the ancillary ligands: the barrier decreases with increasing basicity and decreasing back-donating capability.