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.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry