Comparison of α CH and CF activation in alkyl transition metal complexes: a DFT and CASSCF study

Abstract

DFT (B3PW91) and CASSCF calculations have been carried out to study the relative α migratory abilities of H and F in alkyl transition metal complexes. It is shown that the activation energy is considerably lower to migrate H than F, whereas the energies of reaction are similar for the two reactions. A study of the electron configurations and the orbitals describing these configurations shows that the high activation energy for F is due to a 4-electron repulsion between an F lone pair and the occupied Ru=C π orbital.