The reaction then proceeds with the migration of the -OCH 3 group on another carbon atom of the SV vacancy by means of a pivoting motion around a C-C bond (II-III). The SV structure relaxes, undergoing a distortion which decreases the C-C distance (from 2.5 to 2.0 Å) between the two unsatured carbon atoms (labelled C u1/2 in Fig. ). This process would correspond, considering the C u1 -C u2 bond as formed, to a SV characterized by one fivemembered and one nine-membered ring. Remarkably, the same SV structure has been experimentally observed by TEM on suspendend monolayer Graphene at room pressure and temperature conditions. The system subsequently evolves (III-IV) with the hydrogenation by a methanol molecule of the C u1 atom and consequent formation of a C-H bond pointing towards the methanol.In the next step (IV-V) the shared proton is transferred to the C u2 atom with consequent formation of a -C-H bond pointing toward the bottom Graphene layer.