Significant Differences in the Electrochemical Behavior of the r-, !-, γ-, and δ-Tocopherols (Vitamin E)

R-, !-, γ-, and δ-Tocopherols can be oxidized in dry CH2Cl2 or CH3CN by one electron to form cation radicals that deprotonate to form the neutral phenoxyl radicals, which are then immediately further oxidized by one electron to the phenoxonium cations (an ECE electrochemical mechanism, where E signifies an electron transfer and C represents a chemical step, with the electrochemical mechanism having been determined by in situ spectroscopic analysis). The principal difference in the electrochemical behavior of the tocopherols relates to the stability of their associated phenoxonium cations. The phenoxonium cation of R-tocopherol is stable in solution for at least several hours, the phenoxonium cation of !-tocopherol is stable for several minutes, and the phenoxonium cations of γand δ-tocopherol are stable for <1 s. In dry CH2Cl2 containing >0.75 M acid (CF3COOH), the deprotonation reaction of the cation radicals can be completely inhibited resulting in the cyclic voltammetric behavior of the tocopherols appearing as chemically reversible one-electron oxidation processes (an E mechanism). In dry acid conditions, the cation radicals can be further oxidized by one electron to form the dications, which are unstable and immediately deprotonate. The high stability of the phenoxonium cation of R-tocopherol compared to the other tocopherols (and most other phenols) is a chemically important feature that may shed new light on understanding R-tocopherol’s unique biological properties.