Stability of alkyl carbocations

Chem Commun (Camb). 2022 Oct 27;58(86):12050-12053. doi: 10.1039/d2cc04034d.

Abstract

The traditional and widespread rationale behind the stability trend of alkyl-substituted carbocations is incomplete. Through state-of-the-art quantum chemical analyses, we quantitatively established a generally overlooked driving force behind the stability of carbocations, namely, that the parent substrates are substantially destabilized by the introduction of substituents, often playing a dominant role in solution. This stems from the repulsion between the substituents and the C-X bond.