Mechanism of Alkane C−H Bond Activation by Copper and Silver Homoscorpionate Complexes

DFT Becke3LYP calculations are applied to the computational study of the activation of alkane C−H bonds by metallocarbene homoscorpionate complexes. A total of 16 different combinations of metallocarbene complex and alkane are explored, defined by the use of TpAg C(H)(CO 2 CH 3 ), Tp Br3 Ag C(H)(CO 2 CH 3 ), TpCu C(H)(CO 2 CH 3 ), and Tp Br3 Cu C(H)(CO 2 CH 3 ) species as metallocarbene and methane, ethane, propane, and butane as alkane. The reaction is found to be under kinetic control, and the selectivity is decided in a step with a low-barrier transition state where the key bond-breaking and bond-forming processes take place in a concerted way. This transition state has several possible conformations, which are systematically explored to find the one with lowest energy for each reaction. Variations of the energy barrier as a function of the nature of metal, ligand, and alkane are analyzed and discussed.