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Absolute rate constants for some hydrogen atom abstraction reactions by a primary fluoroalkyl radical in water

From National Research Council Canada

DOIResolve DOI: https://doi.org/10.1039/b313757k
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Affiliation
  1. National Research Council of Canada
FormatText, Article
SubjectAlcohols; Carboxylic acids; Ethers; Fluorine compounds; Hydrogen; Organic solvents; Photolysis; Pulsed laser applications; Rate constants; Water; Absolute rate constant; Bistrifluoromethylbenzene; Fluoroalkyl radical; Hydrogen atom abstraction; Laser flash photolysis; Free radicals
Abstract
A combination of laser flash photolysis and competitive kinetic methods have been used to measure the absolute bimolecular rate constants for hydrogen atom abstraction in water from a variety of organic substrates including alcohols, ethers, and carboxylic acids by the perfluoroalkyl radical, ̇CF2CF2OCF2CF2SO3 -Na+. Comparison, where possible, of these rate constants with those previously measured for analogous reactions in the non-polar organic solvent, 1,3-bis(trifluoromethyl)benzene (J. Am. Chem. Soc, 1999, 121, 7335) show that the alcohols react 2-5 times more rapidly in the water solvent and that the ethers react at the same rate in both solvents. A transition state for hydrogen abstraction that is more reminiscent of an "intimate ion pair" than a "solvent separated ion pair" is invoked to explain these modest solvent effects.
Publication date
In
  • Organic and Biomolecular Chemistry 2, no. 5 (2004): 689–694.
LanguageEnglish
Peer reviewedYes
NPARC number21276455
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Record created2015-10-13
Record modified2020-04-17
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