Homolytic organometallic reactions. Part III. An electron spin resonance study of homolytic t-butoxydealkylation of organometallic compounds. Rate constants for the reaction at boron
- 1 January 1971
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society B: Physical Organic
- p. 1823-1829
- https://doi.org/10.1039/j29710001823
Abstract
When di-t-butyl peroxide is photolysed in the presence of a variety of organometallic compounds (RM) in an e.s.r. cavity, the alkoxyl radicals which are formed induce an SH2 reaction at the metal centre, and the e.s.r. spectrum of the displaced alkyl radical R· can be observed [equation (i)]. The rates of these SH2 reactions for a variety of trialkyl- [graphic omitted] boranes and trialkylboroxines have been studied by causing the organoboranes to compete with cyclopentane for reaction with the t-butoxyl radicals [equation (ii)], and monitoring the relative concentrations of the alkyl and cyclopentyl radicals by e.s.r. The reactions are very fast (ki= 105–107 M–1 s–1) and are characterised by low activation energies (0–5 kcal mol–1), and A factors generally in the range 107–108.Keywords
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