Solvent Effects on C-H Abstraction by Hydroperoxyl Radicals: Implication for Antioxidant Strategies.

ABSTRACT: Kinetic solvent effects (KSE) on hydrogen atom transfer (HAT) reactions play a pivotal role in processes such as photoredox catalysis, electrochemical synthesis, and antioxidant defense. While general principles of KSE are well established, the influence of solvent-radical interactions on the reactivity of the hydroperoxyl radical (HOO^•) remains largely uncharacterized. Here, we examine the effects of noncovalent interactions and acid-base equilibria on HOO^• reactivity, using the autoxidation of 1,4-cyclohexadiene (CHD) as convenient HOO^• source in chlorobenzene (PhCl) or acetonitrile solutions containing cosolvents (S) with varying hydrogen bond acceptor basicities (β₂^H). Equilibrium (K_S) and CHD + HOO^• (<

SUBMITTER: Baschieri A 

PROVIDER: S-EPMC12481551 | biostudies-literature | 2025 Sep

REPOSITORIES: biostudies-literature