A 1,5-Oligosilanylene Dianion as Building Block for Oligosiloxane Containing Cages, Ferrocenophanes, and Cyclic Germylenes and Stannylenes.

Starting out from dipotassium 1,5-oligosiloxanylene diide 2, a 3,7,10-trioxa-octasilabicyclo[3.3.3]undecane was prepared, which represents the third known example of this cage structure type. Reaction of 1,3-dichlorotetramethyldisiloxane with 1,1’-bis[bis(trimethylsilyl)potassiosilyl]ferrocene gave a ferrocenophane with a disiloxane containg bridge. The compound can be further derivatized by conversion into a 1,5-oligosilanyl diide. Reacting 1,5-oligosiloxanylene diide 2 with SnCl2 or GeCl2·dioxane in the presence of PMe3 gave cyclic disilylated tetrylene PMe3 adducts. Release of the base-free stannylene led to a dimerization process which gave a bicyclic distannene as the final product. Abstraction of the PMe3 from the cyclic disilylated germylene PMe3 adduct with B(C6F5)3 caused oxidative addition of the germylene into a para-C-F bond of Me3P·B(C6F5)3.