Computational Study of Ways by Which exo-Silatranes Might Be Prepared.

exo-Silatranes involve cage structures where the nitrogen lone pair points away from the cage rather than into it. This distinguishes them from the well-established endo-silatranes. exo-Silatranes have not been observed experimentally, consistent with a significant benefit to silicon-nitrogen interactions inside the cages as suggested for endo-silatranes. Identifying examples of exo-silatranes would prove useful in understanding Si-N interactions, as they would represent the "no interaction" extreme of the spectrum. We have found four means by which exo-silatranes might be synthesized: (1) employing smaller cages; (2) employing constrained rings to stiffen the cage backbones; (3) employing steric interactions to enhance preference for the less crowded exo-geometry around nitrogen; (4) modifying the Lewis acidity and basicity of the silicon and nitrogen so significantly as to remove their desire to interact. The preference for exo geometries is established using the parameter Δ, representing the distance between the nitrogen atom and the least-squares plane containing the adjacent carbon atoms. In some cases, Δ values for exo-silatranes are greater than 0.3 Å. In others, they are near zero, indicating a nearly planar nitrogen atom. There are no obvious structural markers besides Δ that distinguish between exo- and endo-silatranes.