The mechanism of photochemical 1,3-silyl migration of allylsilane

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Abstract

The photochemical reaction mechanisms of model compounds for 4-tert-butyl-1-(4-phenylphenyl)-1-(1,1-dimethylallyl)silacyclohexane are investigated using a complete active space comprised of six electrons in six orbitals with the standard 6-31G(d) basis set. It is concluded that the stereochemistry in the photochemical 1,3-silyl migrations of allylsilanes has a retention preference, in accord with the Woodward-Hoffmann rules. The calculated conical intersection (CI) structure suggests a dissociation path to radicals in addition to a 1,3-shift path. The bulkiness and rigidness of a silacyclohexane moiety does not affect the stereochemistry, but a slightly elongated Si-C bond length in the CI structure would promote the dissociation path.

Original languageEnglish
Pages (from-to)11902-11906
Number of pages5
JournalJournal of Physical Chemistry A
Volume109
Issue number51
DOIs
Publication statusPublished - 2005 Dec 29

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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