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π–π Catalysis in Carbon Flatland—Flipping [8]Annulene on Graphene
Author(s) -
Kroeger Asja A.,
Karton Amir
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202004045
Subject(s) - catalysis , stacking , non covalent interactions , graphene , hydrogen bond , chemical physics , complementarity (molecular biology) , selectivity , chemistry , cyclooctatetraene , computational chemistry , dispersion (optics) , decomposition , nanotechnology , materials science , molecule , organic chemistry , physics , quantum mechanics , biology , genetics
Noncovalent interactions are an integral part of the modern catalysis toolbox. Although stronger noncovalent interactions such as hydrogen bonding are commonly the main driving force of catalysis, π–π interactions typically provide smaller additional stabilizations, for example, to afford selectivity enhancements. Here, it is shown computationally that pristine graphene flakes may efficiently catalyze the skeletal inversions of various benzannulated cyclooctatetraene derivatives, providing an example of a catalytic process driven solely by π–π stacking interactions. Hereby, the catalytic effect results from disproportionate shape complementarity between catalyst and transition structure compared with catalyst and reactant. An energy decomposition analysis reveals electrostatic and, especially with increasing system size, to a larger extent, dispersion interactions as the origin of stabilization.