π–π Catalysis in Carbon Flatland—Flipping [8]Annulene on Graphene

Abstract Noncovalent interactions are an integral part of the modern catalysis toolbox. Although stronger noncovalent such as hydrogen bonding commonly main driving force catalysis, π–π typically provide smaller additional stabilizations, for example, to afford selectivity enhancements. Here, it is shown computationally that pristine graphene flakes may efficiently catalyze skeletal inversions various benzannulated cyclooctatetraene derivatives, providing example a catalytic process driven solely by stacking interactions. Hereby, effect results from disproportionate shape complementarity between catalyst and transition structure compared with reactant. An energy decomposition analysis reveals electrostatic and, especially increasing system size, larger extent, dispersion origin stabilization.