Journal of the American Chemical Society p. 3519 - 3524 (1988)
Update date:2022-07-30
Topics:
Raner
Lusztyk
Ingold
The free-radical chlorination of alkanes produces polychlorides even at low conversions. These are formed by reaction of chlorine atom/monochloride (or dichloride) geminate pairs. This process has been studied in detail in various solvent systems, and a kinetic scheme has been proposed. Deviations from this scheme have been rationalized as being due to competition between monochloride rotation and reaction of the chlorine atom with reactive molecules in the 'cage walls' surrounding the chlorine atom/chloride geminate pair. Analysis of the dichloride products supports the suggestion that monochloride rotation is not completely 'free' within the lifetime of the geminate pair.
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