DENSITY FUNCTIONAL STUDIES OF THE POTENTIAL ENERGY SURFACE OF THE NI+(CF3)COMPLEX

Abstract The potential energy surface (PES) of [Ni, C, F 3 ] + has been examined by density functional calculations. The global minimum of Ni + (CF 3 ) is found to be a FNi + ⋯F 2 C ion–dipole structure with a calculated bond dissociation energy D 0 (FNi + –F 2 C)=52.5±5.0 kcal/mol. The intact trifluoromethyl isomer, Ni + –CF 3 , and the inserted difluorocarbene isomer, F 2 C–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.