ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
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.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550111103
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