Waking the dead: The SiF32+ dication is a superelectrophile capable of activation of molecules as inert as dinitrogen. It is demonstrated that the reactivity of SiF32+ with neutral molecules M (M=N2, H2, CO, CO2, O2) is determined by formation of intermediates SiF3M2+ and the observed electron transfer is due to a large internal energy stored in the intermediate in the gas phase.