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

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.