A theoretical investigation of the activation of propane by a rhodium catalyst

In this work, we report a theoretical study of the activation of propane by cyclopentadienyl carbonyl rhodium, (Cp)Rh(CO), in order to investigate the selectivity of the activation process. Møller–Plesset perturbation theory up to fourth-order (MP4(SDTQ)) and PBE density functional were used along with coupled-cluster single point calculation on the MP2 optimized geometry (CCSD//MP2) for some processes. It was found that the PBE functional was found particular suitable for the calculation of structural parameters and thermal energy correction. The MP3 and PBE results were found in excellent agreement with the CCSD//MP2 results. According to our calculations, there is no kinetic or thermodynamic discrimination, which would lead to a preferable pathway for the C–H bond activation, with the Gibbs free energy differences involved in the two pathways studied, within 1–2 kcal mol−1.