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, CF2CF2OCF 2CF2SO3 -Na+. The bimolecular rate constants observed for the β-fluorinated alkoxides were in the 105 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.
Date de publication
Organic and Biomolecular Chemistry2, nº 14 (2004) : 2083–2086.