CO Activation Within a Superalkali-Doped Fullerene.

With the aim of finding a suitable synthesizable superalkali species, using the B3LYP/6-31G* density functional level of theory we provide results for the interaction between the buckminsterfullerene C and the superalkali LiF. We show that this endofullerene is stable and provides a closed environment in which the superalkali can exist and interact with CO. It is worthwhile to mention that the optimized LiF structure inside C is not the most stable C isomer found for the "free" superalkali but the D geometry. The binding energy at 0 K between C and LiF (D) is computed to be 119 kJ mol. Once CO is introduced in the endofullerene, it is activated, and the angle is bent to 132. This activation does not follow the previously studied CO reduction by an electron transfer process from the superalkali, but it is rather an actual reaction where a F (from LiF) atom is bonded to the CO. From a thermodynamic analysis, both CO and the encapsulated [LiF⋅CO] are destabilized in C with solvation energies at 0 K of 147 and < -965 kJ mol, respectively.