A real space picture of the role of steric effects in SN2 reactions

Abstract

AbstractWithin substitution reactions, the Bimolecular Nucleophilic Substitution (SN2) reaction mechanism is one of the most frequently found and studied ones. Among other factors, the easiness of the SN2 pathway is classically considered to be determined by steric hindrance. However, the diffuse nature of the latter inevitably darkens these and other arguments holding the pillars of chemical intuition. In this work, we employ the steric energy (EST) descriptor, formulated within the Interacting Quantum Atoms approach, to offer insights regarding this problem. The steric demands of the substrate, nucleophile and leaving group were studied using the gas‐phase SN2 reaction with different organic skeletons (CH3, CH3CH2, (CH3)2CH, (CH3)3C, (CH3)3CCH2) and halogens (F, Cl, and Br) as test‐bed systems. Our results show that, according to EST, the SH experienced along these simple reactions fits, in the general case, the trends predicted by a meticulous and rigorous application of chemic

Aurora Costales Castro

Associate Professor

Associate Professor of Physical Chemistry at the University of Oviedo. Her research applies quantum chemical topology to study chemical bonding in solids, clusters, and molecular systems.