Herein,we disclose an unexpected Si–O–Si cage reorganization that was observed during the standard hydrolytic condensation procedure of tetrasilanol double-decker silsesquioxane(DDSQ)with respective mono-and di-chlo...Herein,we disclose an unexpected Si–O–Si cage reorganization that was observed during the standard hydrolytic condensation procedure of tetrasilanol double-decker silsesquioxane(DDSQ)with respective mono-and di-chlorosilanes.The investigation of this process allowed us to propose the possible mechanism of this transformation.The formation of all structures was confirmed by NMR,FT-IR,and X-ray(for eleven examples)techniques and their thermal stability was verified(TGA).Additionally,we revealed unusual intramolecular homocoupling product formation during the silylative coupling reaction of vinyl-DDSQ derivatives.It deserves to be emphasized that these findings are the first example of a thorough investigation of hydrolytic condensation and the silylative coupling procedures in the chemistry of DDSQs.展开更多
基金funded by the National Science Centre(NCN)grant no UMO-2016/23/B/ST5/00201,UMO-2017/27/N/ST5/00175,and UMO-2020/36/T/ST5/00072 and grants no.POWR.03.02.00-00-I023/17 and POWR.03.02.00-00-I026/16 cofinanced by the European Union through the European Social Fund under the Operational Program Knowledge Education Development.
文摘Herein,we disclose an unexpected Si–O–Si cage reorganization that was observed during the standard hydrolytic condensation procedure of tetrasilanol double-decker silsesquioxane(DDSQ)with respective mono-and di-chlorosilanes.The investigation of this process allowed us to propose the possible mechanism of this transformation.The formation of all structures was confirmed by NMR,FT-IR,and X-ray(for eleven examples)techniques and their thermal stability was verified(TGA).Additionally,we revealed unusual intramolecular homocoupling product formation during the silylative coupling reaction of vinyl-DDSQ derivatives.It deserves to be emphasized that these findings are the first example of a thorough investigation of hydrolytic condensation and the silylative coupling procedures in the chemistry of DDSQs.
