Rate constants for hydrogen abstraction from alkoxides by a perfloroalkyl radical. An oxyanion accelerated process

A combination of laser. ash 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+)-C-.. 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.