DFT Investigation of the Catalytic Hydromethylation of α-Olefins by Metallocenes. 1. Differences between Scandium and Lutetium in Propene Hydromethylation

A DFT study of the catalytic properties of Cp 2 ScCH 3 and Cp 2 LuCH 3 in the hydromethylation of propene has been performed. The catalytic behavior of Cp 2 ScCH 3 is confirmed, and the formation of secondary products is rationalized. It is shown that Cp 2 LuCH 3 cannot exhibit catalytic behavior and that only stoichiometric conversion of propene to isobutane could be observed. The difference in reactivities between the two metallocenes has been investigated, and an electronic explanation is given based on differences in the coordination of propene. However, the intrinsic reactivities of the two metallocenes is proposed to be driven by both electronic and steric effects.