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Digitale Medien

Primary alkyl radicals: Can they be persistent?Issued as NRCC publication No. 17853. (1979)

Griller, David ; Marriott, Paul R.

New York, NY : Wiley-Blackwell

International Journal of Chemical Kinetics 11 (1979), S. 1163-1166

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Details

ISSN: 0538-8066

Schlagwort(e): Chemistry ; Physical Chemistry

Quelle: Wiley InterScience Backfile Collection 1832-2000

Thema: Chemie und Pharmazie

Notizen: The structure of t-Bu3SiċH2, (I), suggested that it might be a persistent primary alkyl radical since it has (i) a bulky group to protect the radical center; (ii) no β-hydrogens, so that a radical-radical disproportionation reaction is impossible; (iii) a β-silicon atom, which should prevent β-scission of tert-butyl as a unimolecular decomposition pathway. However, the self-reaction of (I) in isooctane was found to be a diffusion controlled process with log(A/M-1 sec-1) = 10.7 ± 0.3 and E = 2.5 ± 0.2 kcal mole-1. Hence (I) is not persistent and it is concluded that a persistent primary alkyl will only be observed when the - ĊH2 moiety is deeply buried among sterically protecting groups.

Zusätzliches Material: 1 Ill.

Materialart: Digitale Medien

URL: http://dx.doi.org/10.1002/kin.550111103

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