Institut für Anorganische Chemie, Technische Universität Graz, Stremayrgasse 9, A-8010 Graz, Austria.
Molecules. 2020 Mar 13;25(6):1322. doi: 10.3390/molecules25061322.
Starting out from dipotassium 1,5-oligosiloxanylene diide 2, a 3,7,10-trioxa-octasilabicyclo[3.3.3]undecane was prepared, which represents the third known example of this cage structure type. Reaction of 1,3-dichlorotetramethyldisiloxane with 1,1'-bis[bis(trimethylsilyl)potassiosilyl]ferrocene gave a ferrocenophane with a disiloxane containg bridge. The compound can be further derivatized by conversion into a 1,5-oligosilanyl diide. Reacting 1,5-oligosiloxanylene diide 2 with SnCl or GeCl·dioxane in the presence of PMe gave cyclic disilylated tetrylene PMe adducts. Release of the base-free stannylene led to a dimerization process which gave a bicyclic distannene as the final product. Abstraction of the PMe from the cyclic disilylated germylene PMe adduct with B(CF) caused oxidative addition of the germylene into a para-C-F bond of MeP·B(CF).
从二钾 1,5-寡硅氧烷二聚体 2 出发,制备了 3,7,10-三氧杂-八硅杂双环[3.3.3]十一烷,这是该笼状结构类型的第三个已知实例。1,3-二氯四甲基二硅氧烷与 1,1'-双[双(三甲基甲硅烷基)钾硅基]二茂铁反应得到含有二硅氧烷桥的二茂铁环丙烷。该化合物可以通过转化为 1,5-寡硅基二聚体进一步衍生化。在 PMe 的存在下,将 1,5-寡硅氧烷二聚体 2 与 SnCl 或 GeCl·二氧六环反应,得到 PMe 加合物的环状二硅化三苯乙烯。释放无碱的锡烯导致二聚化过程,最终产物为双环二锡烯。用 B(CF)从环状二硅化锗烯 PMe 加合物中抽去 PMe,导致锗烯对 MeP·B(CF)的对-C-F 键进行氧化加成。