Competition of C–F, C–S, and S–F Bond Activation in SF5CF3 Using N-Heterocyclic Olefins Derivatives: A Computational Study

SF₅CF₃, commonly recognized as a potent greenhouse gas, has recently emerged as a valuable source of fluoride functional groups. Despite its traditional role, recent studies have highlighted its potential applications beyond its environmental implications. However, investigations into its reactivity remain limited, particularly regarding the activation of its constituent bonds. In this study, we conducted a comprehensive computational analysis to elucidate the competition among C–F, C–S, and S–F bond activations within SF₅CF₃ utilizing N-heterocyclic olefin derivatives. Our investigations shed light on the underlying mechanisms of bond activation, revealing a preference for the activation of the S–F bond in SF₅CF₃ by both NHOs and mNHOs. Specifically, we observed a Gibbs free energy barrier (ΔG^≠) ranging from 24.90 to  25.77 kcal/mol in the case of mNHOs, indicating a favorable energetics for this process.