STRUCTURE AND BASICITY OF SILYL ETHERS - A CRYSTALLOGRAPHIC AND ABINITIO INQUIRY INTO THE NATURE OF SILICON OXYGEN INTERACTIONS

Analyses of the Cambridge Structural Database and results of ab initio molecular orbital calculations provide insights into the bond angle widening at oxygen and lowered basicity observed for silyl ethers in comparison to alkyl ethers. Common rationalizations for the phenomena based on interactions of oxygen lone pairs with silicon 3d orbitals and on steric effects do not find support. However, an alternative explanation that considers the detailed nature of the highest occupied molecular orbitals and concepts from Walsh diagrams accounts for the structural and chemical observations in a comprehensive manner. © 1990, American Chemical Society. All rights reserved.