Theoretical exploration of stereochemical nonrigidity for R f Co(PF3) x (CO)4−x (R f =CF3, C2F5, C3F7, x=0–4)

Abstract

The stereochemical nonrigidity of R f Co(PF3) x (CO)4−x (R f =CF3, C2F5, C3F7, x=0–4) was studied at the theoretical level of B3LYP/6-311+G* via Gaussian 09. The intramolecular rearrangements in these penta-coordinated compounds are mainly caused by the vibrations of perfluoroalkyl groups. All the barriers along the reaction coordinate are less than 66.9 kJ/mol, which indicates that the rearrangements are kinetically favorable and hard to elucidate by experiment. Besides, ligand PF3 is a ligand similar to CO, the energy difference between the reactant and product is small.