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On the mechanism of reaction of tert ‐butoxyl radicals with dialkylphosphites
Author(s) -
Brunton G.,
Ingold K. U.
Publication year - 1975
Publication title -
organic magnetic resonance
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0030-4921
DOI - 10.1002/mrc.1270071014
Subject(s) - radical , hydrogen atom abstraction , deuterium , chemistry , kinetic isotope effect , photochemistry , reaction rate constant , hydrogen , reaction mechanism , alkoxy group , spectroscopy , kinetics , organic chemistry , catalysis , alkyl , physics , quantum mechanics
It has been shown by ESR spectroscopy that the title reaction involves abstraction of hydrogen from the phosphite, since at −10°C the reaction has a kinetic deuterium isotope effect, k H /k D , or ∼3. The rate constant for hydrogen abstraction is c . 2 × 10 4 M −1 s −1 . There is no significant addition of alkoxyl radicals to the phosphite.