Pentacoordinate silicon compounds: Stereochemical non-rigidity of chelates formed by intramolecular ring-closure. Crystal structure of 8-dimethylamino-1-trifluorosilylnaphthalene

The application of dynamic NMR spectroscopy to the study of stereochemical non-rigidity in pentacoordinate chelated organosilicon compounds is described. It is shown that in the compounds Me₂ iXYZ, non-dissociative ligand permutation at silicon can be distinguished unambiguously from processes associated with rupture of the chelate ring and nitrogen inversion. The crystal and molecular structure of 8-Me₂NC₁₀H₆SiF₃ has been determined. Pentacoordination of the silicon atom is confirmed, with the donor nitrogen atom and a fluorine atom occupying axial sites in an overall trigonal bipyramidal geometry. The N → Si separation is 2.3 Å (average of two distinct but closely related molecular conformations), which is less than the C¹---C⁸ distance in the naphthalene nucleus, indicating a substantial bonding interaction. NMR studies of the dynamic behaviour of the Me₂N group, and where possible (¹⁹F, ¹H) of the monodentate ligands in 8-dimethylamino-1-silylnaphthalene compounds, together with the results for the chelated benzylaminosilicon compounds, confirm that inversion of the absolute configuration at the silicon atom is not achieved by this process. The free energies of activation for non-dissociative ligand permutation at a silicon range from less than 7 kcal mol⁻¹ SiH₃, Si(OR)₃], which is below the limit of direct measurement, to 13 kcal mol⁻¹ for Me₂NCH(Me)C₆H₄SiF₃; difunctional silicon chelate compounds (Cl, F, OR) display values from 9–12 kcal mol⁻¹. These are comparable with those determined for fluxional processes in acyclic pentacoordinate silicon compounds.