Stefanowska Kinga, Szyling Jakub, Walkowiak Jędrzej, Franczyk Adrian
Center for Advanced Technology, Adam Mickiewicz University in Poznań, Uniwersytetu Poznańskiego 10, 61-614 Poznań, Poland.
Faculty of Chemistry, Adam Mickiewicz University in Poznań, Uniwersytetu Poznańskiego 8, 61-614 Poznań, Poland.
Inorg Chem. 2021 Aug 2;60(15):11006-11013. doi: 10.1021/acs.inorgchem.1c00689. Epub 2021 Jun 16.
Trifunctional incompletely condensed polyhedral oligomeric silsesquioxanes (RSiMeO)R'SiO (s) are considered as intriguing building nanoblocks dedicated to constructing highly advanced organic-inorganic molecules and polymers. Up to now, they have been mainly obtained 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 structure. Therefore, in this work, we present a highly selective and efficient synthesis of the first example of tripodal alkenyl-functionalized s, obtained platinum-catalyzed hydrosilylation of the terminal and internal alkynes, as well as symmetrically and nonsymmetrically 1,4-disubstituted buta-1,3-diynes with silsesquioxanes (HSiMeO)R'SiO (R' = -CH (), (HC)CHC(HC)HCHC ()). The resulting products are synthetic intermediates that contain C═C bonds and functional groups (e.g., OSiMe, SiR, Br, F, B(O(C(CH)) (Bpin)), thienyl), which make them suitable for application in the synthesis of novel, complex, hybrid materials with unique properties.
三官能团不完全缩合的多面体低聚倍半硅氧烷（RSiMeO）R'SiO（s）被认为是用于构建高度先进的有机-无机分子和聚合物的有趣的纳米结构单元。到目前为止，它们主要通过烯烃的硅氢加成反应获得，而C≡C键的硅氢加成反应尚未得到研究，尽管这种方法具有巨大的潜力，因为有可能将3个、6个甚至更多的官能团引入结构中。因此，在这项工作中，我们展示了一种高度选择性和高效的合成方法，首次通过铂催化末端和内炔烃以及对称和非对称1,4-二取代丁-1,3-二炔与倍半硅氧烷（HSiMeO）R'SiO（R' = -CH（），（HC）CHC（HC）HCHC（））的硅氢加成反应，得到了三脚架烯基官能化s的第一个实例。所得产物是含有C═C键和官能团（例如，OSiMe、SiR、Br、F、B（O（C（CH））（Bpin））、噻吩基）的合成中间体，这使得它们适用于合成具有独特性能的新型、复杂的杂化材料。
