First, we performed a fast, prejudice-free exploration of the possible reactive channels at the BLG/methanol interface by applying the metadynamics bias in the space of SPRINT (social permutation invariant) collective variables. The latter, obtained by diagonalizing a smooth interatomic adjacency matrix, capture the changes in atomic-bond topology and proved effective in discovering structural transformations in many systems, including covalent carbon networks. This approach allowed us to identify several chemical reaction pathways, that were further investigated, including estimation of the associated free energy barriers and metadynamics with smooth coordination numbers as well as with path collective variables based on patterns of coordination numbers. The details about the metadynamics protocols can be found in Supporting Information. The input files of CP2K and Plumed for the simulations in this work, as well as selected atomic configurations (metastable states at 300 K and different pressures), are freely available from Plumed Nest. The Electron Localization Function (ELF) for each reactive structure was calculated using CP2K, following the same setup as the one used for the dynamics simulations. The automatic identification of ELF critical points (AUTO) was carried out using the Wigner-Seitz cell (WS) and pairs