Cubic Siloxanes with Both Si-H and Si-OtBu Groups for Site-Selective Siloxane Bond Formation.

Cage-type siloxanes have attracted increasing attention as building blocks for silica-based nanomaterials as their corners can be modified with various functional groups. Cubic octasiloxanes incorporating both Si-H and Si-OtBu groups [(tBuO)n H8-n Si8 O12 ; n=1, 2 or 7] have been synthesized by the reaction of octa(hydridosilsesquioxane) (H8 Si8 O12 ) and tert-butyl alcohol in the presence of a Et2 NOH catalyst. The Si-H and Si-OtBu groups are useful for site-selective formation of Si-O-Si linkages without cage structure deterioration. The Si-H group can be selectively hydrolyzed to form a Si-OH group in the presence of Et2 NOH, enabling the formation of the monosilanol compound (tBuO)7 (HO)Si8 O12 . The Si-OH group can be used for either intermolecular condensation to form a dimeric cage compound or silylation to introduce new reaction sites. Additionally, the alkoxy groups of (tBuO)7 HSi8 O12 can be treated with organochlorosilanes in the presence of a BiCl3 catalyst to form Si-O-Si linkages, while the Si-H group remains intact. These results indicate that such bifunctional cage siloxanes allow for stepwise Si-O-Si bond formation to design new siloxane-based nanomaterials.