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The Supporting Information of the following paper shows CVs of a number of phenylenediamines in acetonitrile
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84885918227
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note
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a's in Scheme 1) removes the "trap" at the low concentrations, resulting in a simulated CV similar to that seen at higher concentrations. We have extensively explored other possible mechanisms involving only solution-phase chemical steps but have not been able to come up with one that includes all likely reactions and gives, even qualitatively, the observed concentration dependence.
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A similar geometry has been reported before for the doubly oxidized form of the completely methylated analogue, N,N,N′,N′-2,3,5,6- octamethylphenylene. In this case, steric hindrance between the C-Me H's and the N-Me H's in the quinoidal state forces the bending. It is also interesting to note that the oxidation of this compound is one of the rare examples of a single 2 e-process in nonaqueous solutions. This is because the intermediate radical state is destabilized more by the steric effects than the fully reduced or fully oxidized forms
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A similar geometry has been reported before for the doubly oxidized form of the completely methylated analogue, N,N,N′,N′-2,3,5,6- octamethylphenylenediamine. In this case, steric hindrance between the C-Me H's and the N-Me H's in the quinoidal state forces the bending. It is also interesting to note that the oxidation of this compound is one of the rare examples of a single 2 e-process in nonaqueous solutions. This is because the intermediate radical state is destabilized more by the steric effects than the fully reduced or fully oxidized forms. Gruhn, N. E.; Macias-Ruvalcaba, N. A.; Evans, D. H. J. Phys. Chem. A 2006, 110, 5650-5655
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Gruhn, N.E.1
Macias-Ruvalcaba, N.A.2
Evans, D.H.3
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84885923156
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note
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