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.
Cedrowski, J., Litwinienko, G., Baschieri, A., Amorati, R. (2016). Hydroperoxyl Radicals (HOO.): Vitamin E Regeneration and H-Bond Effects on the Hydrogen Atom Transfer. CHEMISTRY-A EUROPEAN JOURNAL, 22(46), 16441-16445 [10.1002/chem.201603722].
Hydroperoxyl Radicals (HOO.): Vitamin E Regeneration and H-Bond Effects on the Hydrogen Atom Transfer
BASCHIERI, ANDREA;AMORATI, RICCARDO
2016
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.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
