Kroeger Asja A, Karton Amir
School of Molecular Sciences, The University of Western Australia, 35 Stirling Highway, Crawley, WA, 6009, Australia.
Chemistry. 2021 Feb 15;27(10):3420-3426. doi: 10.1002/chem.202004045. Epub 2021 Jan 21.
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.
非共价相互作用是现代催化工具箱中不可或缺的一部分。虽然更强的非共价相互作用（如氢键）通常是催化的主要驱动力，但π-π相互作用通常提供较小的额外稳定性，例如用于提高选择性。在此，通过计算表明，原始石墨烯薄片可以有效地催化各种苯并环辛四烯衍生物的骨架反转，提供了一个仅由π-π堆积相互作用驱动的催化过程的例子。因此，催化效应源于催化剂与过渡结构之间的形状互补性与催化剂和反应物之间的不成比例。能量分解分析表明，静电作用，特别是随着体系尺寸的增加，在更大程度上，色散相互作用是稳定性的来源。
