Absolute kinetics of aminium radical reactions with ...

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Title Absolute kinetics of aminium radical reactions with olefins in acetonitrile solution
Author(s) Brian D. Wagner, G. Ruel, J. Lusztyk
Journal Journal of the American Chemical Society
Date 1996
Volume 118
Issue 1
Start page 13
End page 19
Abstract Abstract: Photolysis of N-nitrosamines in acidic acetonitrile produces aminium radical cations via protonation of the initially-formed aminyl radicals. The kinetics of these species can be monitored by transient UV spectroscopy via their absorption band which is found at ca. 300 nm in the case of the piperidinium radical, for example. By measuring the aminium radicals' lifetimes as a function of the concentration of added olefin, absolute values for the bimolecular rate constants for the addition reactions were obtained. In the case of the piperidinium radical, these rate constants varied from 1 ? 108 s-1 upon the phenyl substitution at the olefinic terminus.
DOI 10.1021/ja950133y

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