| Résumé | The rate of hydrogen-atom abstraction from XH by a radical, Y•, can be solvent-dependent. In many cases, the kinetic solvent effect (KSE) is directly related to hydrogen-bonding interactions between XH and the solvent. The relative hydrogen-bond acceptor (HBA) properties of solvents are given by constants of Abraham et al. (Abraham, M. H.; Grellier, P. L.; Prior, D. V.; Morris, J. J.; Taylor, P. J. J. Chem. Soc. Perkin Trans. 2 1990, 521−529). Room-temperature rate constants for hydrogen-atom abstraction, , have been determined in a number of solvents, S, where XH refers to several substituted phenols, tert-butyl hydroperoxide or aniline and Y• is a tert-alkoxyl radical. In all cases, plots of log( /M-1 s-1) versus gave excellent linear correlations, the slopes of which, MXH, were found to be proportional to the hydrogen-bond-donating (HBD) ability of XH, as scaled with parameters of Abraham et al. (Abraham, M. H.; Grellier, P. L.; Prior, D. V.; Duce, P. P.; Morris, J. J.; Taylor, P. J. J. Chem. Soc., Perkin Trans. 2 1989, 699−711), with MXH = − 8.3 . This leads to a general empirical equation which quantifies KSEs at room temperature: log = log − 8.3 , where refers to the rate constant in a non-HBA solvent for which = 0, generally a saturated hydrocarbon. Since MXH depends only on XH, rate constants for hydrogen-atom abstraction from XH by any Y• can be accurately predicted in any of the several hundred solvents for which is known on the basis of one single measured rate constant, provided for XH is known or measured. HBA solvents can have profound effects on some of the reactions and thermodynamic properties of hydroxylic substrates including: (i) reaction product profiles (ii) antioxidant activities, (iii) Hammett-type correlations, and (iv) O−H bond dissociation enthalpies. Finally, literature data (Nielsen, M. F.; Hammerich, O. Acta Chem. Scand, 1992, 46, 883−896) on KSEs for two proton-transfer reactions are shown to be correlated by the same equation which correlates KSEs for hydrogen-atom transfers. |
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