Cleaving a C–F bond of C6F6 at a gallium(i) centre catalyzed by nitrogen-containing Lewis bases and its kinetic analysis

Gallylenes, gallium(I) molecules in the oxidation state of +1, supported by a NacNac or Boxm ligand, underwent an efficient C-F bond cleavage of C₆F₆ upon addition of a stoichiometric/catalytic amount of nitrogen-containing Lewis bases (LBs). Kinetic studies revealed that the C-F bond cleavage was first-order in terms of the concentrations of gallylene and the added nitrogen-containing LBs. The reaction rate also depended on the nitrogen-containing LBs. DFT calculations indicated that the coordination of nitrogen-containing LBs to the Ga centre increased the energy level of the HOMO, which was contributed by a lone pair of electrons at the Ga centre. These results underscore the utility of Lewis base modulation in main-group-mediated bond cleavage.