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Another relevant reaction that causes the decay of the semiquinone radical is the disproportionation of two semiquinone radicals, •QH, to give the quinone (Q) and hydroquinone (QH2, However, this reaction (eq 9) does not affect the stoichiometric factor with respect to the trapping of a second peroxyl radical by the semiquinone (eq 8, i.e, n, 2 not necessarily as written
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The calculated solvent effect on the elimination of HOO• is 3.3 kcal/mol. While this is larger than the observed effect on the rate constant roughly one order of magnitude, it should be noted that in our calculations we are comparing the isolated O2-adduct in the gas phase with the O2-adduct H-bonded to HCN in the gas phase. It is totally reasonable that this would be overestimated relative to the O2 adduct H-bonded to chlorobenzene compared to the O2-adduct H-bonded to acetonitrile in our experiments
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2-adduct H-bonded to acetonitrile in our experiments.
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16244368454
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2 = 0.37 for the reaction intermediate, in excellent agreement with the values obtained in the present work. In that paper a somewhat similar reaction mechanism was also tentatively suggested, i.e., a cyclic transition state with the oxygen complexed to the π system of the aromatic ring. We thank Dr. Peter Mulder for pointing out this reference.
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2 = 0.37 for the reaction intermediate, in excellent agreement with the values obtained in the present work. In that paper a somewhat similar reaction mechanism was also tentatively suggested, i.e., a cyclic transition state with the oxygen complexed to the π system of the aromatic ring. We thank Dr. Peter Mulder for pointing out this reference.
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