Density functional studies of the potential energy surface of the Ni+(CF3) complex

The potential energy surface (PES) of [Ni, C, F3]+ has been examined by density functional calculations. The global minimum of Ni+(CF3) is found to be a FNi+⋯F2C ion–dipole structure with a calculated bond dissociation energy D0(FNi+–F2C)=52.5±5.0 kcal/mol. The intact trifluoromethyl isomer, Ni+–CF3, and the inserted difluorocarbene isomer, F2C–Ni+–F, are located at higher energies on the PES. The transition state structures connecting these minima are optimized and the largest barrier of the system, 13.6 kcal/mol, involves C–F activation.