Journal of the American Chemical Society p. 128 - 133 (1986)
Update date:2022-08-10
Topics:
Naguib, Yousry M. A.
Cohen, Saul G.
Steel, Colin
Crystal violet (CV+) is stable to direct photolysis in acetonitrile at λirr >/= 366 nm even in the presence of hydrogen donors (benzhydrol and 2-propanol).However, when benzophenone (K) is present in samples containing hydrogen donor and λirr = 366 nm, sensitized photofading occurs.On the basis of chemical evidence and the concentration and intensity dependence of the sensitized quantum yields, a one-electron reduction of CV+ by diphenylketyl (KH.) followed by hydrogen transfer to the intermediate CV. with formation of the leuco dye (CVH) is proposed.The rate constant (k6) for the electron transfer reaction CV+ + KH. -> CV. + K + H+, k6 = 6 +/- 2 x 105 M-1 s-1 (6) has been determined by two methods both of which rely on the competition between reactions 5 and 6 2KH. -> K2H2, k5 = 1.05 +/- 0.02 x 108 M-1 s-1 (5) In the first the quantum yield of sensitized fading is determined as a function of CV+ concentration.In the second the rates of benzpinacol formation in the absence and presence of CV+ are followed.
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