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more..
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38
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79953838085
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note
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. radicals.
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40
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0001652762
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Using the B971 functional, as implemented in ref 27, along with 6-31〈G(d,p) basis sets
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For a critical discussion of the role of structural effects on the ET reactions of ?-stacked systems, see: Rosokha, S. V.; Kochi, J. K. J. Am. Chem. Soc. 2007, 129, 3683-3697.
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In ref 33, the kinetic plots of kobs vs [ArH] for unhindered donors showed an asymptotic behavior diagnostic of a preequilibrium step that precedes ET. From these plots the preequilibrium constant (KEC) and the intrinsic ET rate constant (kET) could be obtained. Linear plots of kobs vs [MenFc] have been instead obtained for the reactions of the 4-X-CumO. radicals, where the relatively strong absorption of the ferrocene donors at the laser excitation wavelength limited the study to [MenFc] ≤ 5 mM (see the Supporting Information). Accordingly, at these low concentrations the measured second order rate constant can be expressed as k2 = KECkET. On the basis of this kinetic scheme, and on the data collected in Table 1, spectral evidence for the formation of an encounter complex would require significantly higher concentrations of the ferrocene donors. See, for example: Rathore, R.; Hubig, S. M.; Kochi, J. K. J. Am. Chem. Soc. 1997, 119, 11468-11480.
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