Polar Effects in Hydrogen Atom Transfer Reactions from a Proton-Coupled Electron Transfer (PCET) Perspective: Abstractions from Toluenes.

ABSTRACT: Rate constants for hydrogen atom transfer (HAT) reactions of substituted toluenes with tert-butyl, tert-butoxy, and tert-butylperoxyl radicals are reanalyzed here using the free energies of related proton transfer (PT) and electron transfer (ET) reactions, calculated from an extensive set of compiled or estimated pK_a and E° values. The Eyring activation energies ΔG_HAT^‡ do not correlate with the relatively constant ΔG°_HAT, but do correlate close-to-linearly with ΔG°_PT and ΔG°_ET. The slopes of correlations are similar for the three radicals except that the ^tBu^• barriers shift in the opposite direction from the oxyl radical barriers─a cl

SUBMITTER: Groff BD 

PROVIDER: S-EPMC10841608 | biostudies-literature | 2023 Dec

REPOSITORIES: biostudies-literature