Abstract
Trifunctional incompletely condensed polyhedral oligomeric silsesquioxanes (RSiMe(2)O)(3)R'(7)Si(7)O(9) (IC-POSSs) are considered as intriguing building nanoblocks dedicated to constructing highly advanced organic-inorganic molecules and polymers. Up to now, they have been mainly obtained via hydrosilylation of olefins, while the hydrosilylation of the C≡C bonds has not been studied at all, despite the enormous potential of this approach resulting from the possibility of introducing 3, 6, or even more functional groups into the IC-POSS structure. Therefore, in this work, we present a highly selective and efficient synthesis of the first example of tripodal alkenyl-functionalized IC-POSSs, obtained via platinum-catalyzed hydrosilylation of the terminal and internal alkynes, as well as symmetrically and nonsymmetrically 1,4-disubstituted buta-1,3-diynes with silsesquioxanes (HSiMe(2)O)(3)R'(7)Si(7)O(9) (R' = i-C(4)H(9) (1a), (H(3)C)(3)CH(2)C(H(3)C)HCH(2)C (1b)). The resulting products are synthetic intermediates that contain C═C bonds and functional groups (e.g., OSiMe(3), SiR(3), Br, F, B(O(C(CH(3))(2))(2) (Bpin)), thienyl), which make them suitable for application in the synthesis of novel, complex, hybrid materials with unique properties.