Fluoride catalyzed rearrangements of polysilsesquioxanes, mixed Me, vinyl T8, Me, vinyl T10 and T12 cages

Insoluble mixtures of polyvinylsilsesquioxane, -(vinylSiO(1.5))(n)-PVS, and polymethylsilsesquioxanes, -(MeSiO1.5)(n)-PMS, in THF at ambient when treated with catalytic amounts (1-5 mol%) of fluoride ion introduced as tBu(4) NF will depolymerize and dissolve. The resulting soluble species consist of [vinyl(x)Me(8-x)(SiO1.5)](8), [vinyl(x)Me(8-x)(SiO1.5)](10) and [vinyl(x)Me(8-x)(SiO1.5)](12). Ratios of 1 : 1 of PVS : PMS greatly favor formation of vinyl rich cages. Only at ratios of 1 : 5 are the proportions of vinyl : Me in the cages approximately equal. Of the T-8, T-10 and T-12 species produced, all conditions tried, including changing the solvent to EtOH or toluene or at reflux (THF), favor the formation of the larger cages sometimes completely excluding formation of the T-8 materials. Efforts to isolate the cage compounds by removal of solvent regenerates polysilsesquioxanes, albeit those containing mixtures of Me and vinyl groups. Introduction of CaCl2 sufficient to form CaF2 prior to workup prevents repolymerization, allowing recovery of the mixed cage systems. The approach developed here provides a novel way to form mixed functional group silsesquioxane cages. The fact that T-10 and T-12 cage formation is favored appears to suggest that these cages are more stable than the traditionally produced T-8 cages. Copyright (C) 2009 John Wiley & Sons, Ltd.