title: Rate constants for hydrogen abstraction from alkoxides by a perfluoroalkyl radical. An oxyanion accelerated process.
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.
authors.affiliation: Department of Chemistry, University of Florida, Gainesville, FL 32611-7200, USA.
authors.forename: Joseph A
authors.initials: JA
authors.lastname: Cradlebaugh
authors.forename: Li
authors.initials: L
authors.lastname: Zhang
authors.forename: G Robert
authors.initials: GR
authors.lastname: Shelton
authors.forename: Grzegorz
authors.initials: G
authors.lastname: Litwinienko
authors.forename: Bruce E
authors.initials: BE
authors.lastname: Smart
authors.forename: Keith U
authors.initials: KU
authors.lastname: Ingold
authors.forename: William R
authors.initials: WR
authors.lastname: Dolbier