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Rate constants for the bimolecular self-reaction of cyano-substituted alkyl radicals in solution

✍ Scribed by H. G. Korth; P. Lommes; W. Sicking; R. Sustmann

Publisher
John Wiley and Sons
Year
1983
Tongue
English
Weight
639 KB
Volume
15
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

Cyano‐substituted methyl radicals (cyanomethyl–hand 2‐cyano‐2‐propyl radicals) and syn‐and anti‐1‐cyano‐allyl radicals were generated, and their recombination kinetics in solution were investigated between −50 and +50°C by time‐resolved electron‐spin‐resonance spectroscopy. The comparison of the activation energies for recombination with the activation energies of the solution viscosities proves that the dimerizations of the radicals are diffusion controlled with rate constants on the order of 10^8^–10^9^M^−1^·s^−1^. In the case of cyanomethyl radicals an additional pseudo‐first‐order process, hydrogen abstraction, was detected and analyzed kinetically. Product analyses support the kinetic measurements.

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