Hydroperoxyl Radicals (HOO^.): Vitamin E Regeneration and H‐Bond Effects on the Hydrogen Atom Transfer

Abstract

Hydroperoxyl (HOO^. ) and alkylperoxyl (ROO^. ) radicals show a different behavior in H-atom-transfer processes. Both radicals react with an analogue of α-tocopherol (TOH), but HOO^. , unlike ROO^. , is able to regenerate TOH by a fast H-atom transfer: TO^. +HOO^. →TOH+O₂ . The kinetic solvent effect on the H-atom transfer from TOH to HOO^. is much stronger than that observed for ROO^. because noncovalent interactions with polar solvents (Solv⋅⋅⋅HOO^. ) destabilize the transition state.