Density functional study for the C–F bond activation of the reaction of [Pt(PCy3)2] with C6F6

The mechanisms for C–F bond activation of the reaction of [Pt(PCy3)2] of C6F6, which yields metal–aryl product, have been characterized. Structures and energies for all of the stationary points in the [Pt(PMe3)2] and [Pt(PH3)(PH2Me)] models have been calculated using BP86 method. The calculated results show that the [Pt(PMe3)2] model is a more adequate for simulating the real system compared to the [Pt(PH3)(PH2Me)] model. The calculations also reveal that the concerted phosphine-assisted mechanism (pathway A) proceeding through the transfer of fluorine with the simultaneous shift of the Me group is the most accessible mechanism in the gas phase and in THF to form the Pt-aryl product, while the stepwise phosphine-assisted mechanisms (pathway B) and a mechanism via concerted oxidative addition (pathway C) proved less favorable. The further computational studies on the reaction of the model system [Pd(PMe3)2]) with C6F6 indicate the Pd-fluoroaryl product is more accessible than the Pd-aryl product.