Rate constants for hydrogen abstraction from alkoxides by a perfluoroalkyl radical. An oxyanion accelerated processElectronic supplementary information (ESI) available: Tables of kinetic data and plots of kinetic data. See http://www.rsc.org/suppdata/ob/b4/b405074f
Organic & Biomolecular Chemistry2004Vol. 2(14), pp. 2083–2083
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Joseph A. Cradlebaugh, Li Zhang, G. Robert Shelton, Grzegorz Litwinienko, Bruce E. Smart, K. U. Ingold, William R. Dolbier
Abstract
A combination of laser flash photolysis and competitive kinetic methods has been used to measure the absolute bimolecular rate constants for hydrogen atom abstraction in water from a series of fluorinated alkoxides and aldehyde hydrates by the perfluoroalkyl radical, *CF2CF2OCF2CF2SO3- Na+. The bimolecular rate constants observed for the beta-fluorinated alkoxides were in the 10(5) M(-1) s(-1) range, such rates representing enhancements (relative to the respective alcohols) of between 100 and almost 1000-fold, depending on the reactivity of the alkoxide. Likewise, the monobasic sodium salts of chloral and fluoral hydrate exhibit similar rate enhancements, relative to their respective hydrates.
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