Premium
Unusual selectivities of radical reactions. Experimental studies on alkyl versus phenoxyl reaction systems
Author(s) -
Rüegge Daniel,
Fischer Hanns
Publication year - 1989
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550210809
Subject(s) - chemistry , radical , alkyl , photochemistry , reaction rate constant , hydrogen atom , reaction intermediate , kinetics , organic chemistry , catalysis , physics , quantum mechanics
Radical reactions involving two or more intermediates and many mutual reaction channels may lead to the specific formation of one cross‐reaction product if one species is rather persistent and if transient and persistent species are produced with equal rates. A previous kinetic analysis of the phenomenon revealed that the concentrations of the intermediates and the selectivities of product formation depend critically on the relative initiation rates. The present experimental ESR studies on systems involving simultaneously generated phenoxyl radicals as persistent and alkyl radicals as transient species confirm the predicted behavior. They also lead to absolute rate constants for reactions of alkyl with phenoxyl radicals and for hydrogen atom transfer from phenols to alkyl radicals.