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