Notable Effects of the Metal Salts on the Formation and Decay Reactions of α-Tocopheroxyl Radical in Acetonitrile Solution. The Complex Formation between α-Tocopheroxyl and Metal Cations

The measurement of the UV-vis absorption spectrum of alpha-tocopheroxyl (alpha-Toc(center dot)) radical was performed by reacting aroxyl (ArO(center dot)) radical with alpha-tocopherol (alpha-TocH) in acetonitrile solution including four kinds of alkali and alkaline earth metal salts (MX or MX(2)) (LiClO(4), LiI, NaClO(4), and Mg(ClO(4))(2)), using stopped-flow spectrophotometry. The maximum wavelength (lambda(max)) of the absorption spectrum of the alpha-Toc(center dot) at 425.0 nm increased with increasing concentration of metal salts (0-0.500 M) in acetonitrile, and it approached constant values, suggesting an [alpha-Toc(center dot)- M(+) (or M(2+))] complex formation. The stability constants (K) were determined to be 9.2, 2.8, and 45 M(-1) for LiClO(4), NaClO(4), and Mg(ClO(4))(2), respectively. By reacting ArO(center dot) with alpha-TocH in acetonitrile, the absorption of ArO(center dot) disappeared rapidly, while that of alpha-Toc(center dot) appeared and then decreased gradually as a result of the bimolecular self-reaction of alpha-Toc(center dot) after passing through the maximum. The second-order rate constants (k(s)) obtained for the reaction of alpha-TocH with ArO(center dot) increased linearly with an increasing concentration of metal salts. The results indicate that the hydrogen transfer reaction of alpha-TocH proceeds via an electron transfer intermediate from alpha-TocH to ArO(center dot) radicals followed by proton transfer. Both the coordination of metal cations to the one-electron reduced anions of ArO(center dot) (ArO:(-)) and the coordination of counteranions to the one-electron oxidized cations of alpha-TocH (alpha-TocH(center dot+)) may stabilize the intermediate, resulting in the acceleration of electron transfer. A remarkable effect of metal salts on the rate of bimolecular self-reaction (2k(d)) of the alpha-Toc(center dot) radical was also observed. The rate constant (2k(d)) decreased rapidly with increasing concentrations of the metal salts. The 2k(d) value decreased at the same concentration of the metal salts in the following order: no metal salt > NaClO(4) > LiClO(4) > Mg(ClO(4))(2). The complex formation between alpha-Toc(center dot) and metal cations may stabilize the energy level of the reactants (alpha-Toc(center dot) + alpha-Toc(center dot)), resulting in the decrease of the rate constant (2k(d)). The alkali and alkaline earth metal salts having a smaller ionic radius of cation and a larger charge of cation gave larger K and k(s) values and a smaller 2k(d) value.