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

Download
  1. Get@NRC: Absolute rate constants for some hydrogen atom abstraction reactions by a primary fluoroalkyl radical in water (Opens in a new window)
DOIResolve DOI: http://doi.org/10.1039/b313757k
AuthorSearch for: ; Search for: ; Search for: ; Search for: ; Search for: ; Search for:
TypeArticle
Journal titleOrganic and Biomolecular Chemistry
ISSN1477-0520
Volume2
Issue5
Pages689694; # of pages: 6
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
AbstractA 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
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276455
Export citationExport as RIS
Report a correctionReport a correction
Record identifierda2be234-0a9a-4af2-9160-e4423171b44a
Record created2015-10-13
Record modified2016-05-09
Bookmark and share
  • Share this page with Facebook (Opens in a new window)
  • Share this page with Twitter (Opens in a new window)
  • Share this page with Google+ (Opens in a new window)
  • Share this page with Delicious (Opens in a new window)