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Nucleophilic character of the tert ‐butyl radical. Absolute rate constants for the reactions with substituted toluenes
Author(s) -
Dütsch H. R.,
Fischer H.
Publication year - 1982
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.550140209
Subject(s) - chemistry , reaction rate constant , nucleophile , radical , substituent , photochemistry , yield (engineering) , medicinal chemistry , spectroscopy , hydrogen , kinetics , catalysis , organic chemistry , physics , quantum mechanics , materials science , metallurgy
The decay of photochemically generated tert ‐butyl radicals is studied at 48°C in 11 m ‐ and p ‐substituted toluenes by time‐resolved electron spin resonance spectroscopy. It is governed by the second‐order self‐termination perturbed by a pseudo‐first‐order reaction of the radical with the toluenes. The first‐order lifetimes yield the rate constants k A for hydrogen transfer from toluenes to tert ‐butyl. Substituent effects on the rate constants confirm the nucleophilic character of the radical.