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Issue 1, 2003
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1,2-Chlorine atom migration in 3-chloro-2-butyl radicals: a computational study

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Abstract

Skell’s hypothesis of bridged 2-haloalkyl radicals has been revisited using several different theoretical methods and the 3-chloro-2-butyl radical as an example.

The structure as well as several unimolecular reaction pathways of the 3-chloro-2-butyl radical 1 have been studied at several different theoretical levels (B3LYP/aug-cc-pVDZ, BHLYP/aug-cc-pVDZ, G3(ROMP2)B3). The symmetrically chlorine-bridged structure is a transition state at all levels of theory and the most favorable ground state structure is the unbridged β-chloroalkyl radical. Reaction barriers for the 1,2-chlorine migration process are higher than those for rotation around the central C–C bond. 1,2-migration of the chlorine atom is accompanied by an increase in chlorine negative charge as well as chlorine spin density. This hybrid homo-/heterolytic process is well known from rearrangement reactions in β-(dialkoxyphosphoryloxy)alkyl radicals and suggests that chlorine migration can be influenced by polar substituent effects.

Graphical abstract: 1,2-Chlorine atom migration in 3-chloro-2-butyl radicals: a computational study

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Publication details

The article was received on 05 Aug 2002, accepted on 22 Oct 2002 and first published on 26 Nov 2002


Article type: Paper
DOI: 10.1039/B209981K
Org. Biomol. Chem., 2003,1, 168-172

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    1,2-Chlorine atom migration in 3-chloro-2-butyl radicals: a computational study

    B. Neumann and H. Zipse, Org. Biomol. Chem., 2003, 1, 168
    DOI: 10.1039/B209981K

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