Abstract
Hexacoordinate silicon bis chelates with the SiC2O2N2 ligand framework have been prepared, with different nitrogen-donor ligands, NMe2 and NCMe2. Crystal diffraction analyses revealed that the former type had a bicapped-tetrahedral geometry and the latter an octahedral molecular geometry in the solid state. The two N→Si dative bonds in the isopropylideneimino-coordinated compound are sufficiently strong to change silicon from its tetrahedral ground-state configuration to the higher energy octahedral configuration. In contrast, the weaker NMe2 donor groups do not form strong enough bonds to cause this change, and as a result silicon remains tetrahedral and forms only substantially longer and weaker N→Si dative bonds (2.7−2.8 A). Remote electron-releasing NMe2 substituents on the chelate rings render the ligand NMe2 groups stronger donors, resulting in reversal of the solid-state geometry back to octahedral. 29Si, 1H, and 13C NMR spectra at various temperatures provide evidence for the coexistence in equili...
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