Department of Chemistry and Analytical Sciences, Open University, Walton Hall, Milton Keynes, UK MK7 6AA.
Dalton Trans. 2012 Feb 21;41(7):2048-59. doi: 10.1039/c1dt11340b. Epub 2011 Dec 19.
A range of fluoride-encapsulated octasilsesquioxane cage compounds have been prepared using the TBAF route. Our studies suggest that whilst it is relatively straightforward to prepare fluoride-encapsulated octasilsesquioxane cage compounds with adjacent sp(2) carbons, leading to a range of aryl and vinyl substituted compounds, the corresponding sp(3) carbon derivatives are more capricious, requiring an electron withdrawing group that can stabilize the cage whilst not acting as a leaving group. Analysis by X-ray crystallography and solution (19)F/(29)Si NMR spectroscopy of R(8)T(8)@F(-) reveal very similar environments for the encapsulated fluoride octasilsesquioxane cages. Migration of a fluoride ion from inside the cage to outside the cage without breaking the T(8) framework and the possibility of encapsulating other anions within silsesquioxane cages have been also investigated.
已使用 TBAF 路线制备了一系列含氟八硅倍半氧烷笼状化合物。我们的研究表明，虽然相对容易制备具有相邻 sp(2)碳原子的含氟八硅倍半氧烷笼状化合物，从而得到一系列芳基和乙烯基取代的化合物，但相应的 sp(3)碳衍生物则更加复杂，需要一个吸电子基团，该基团可以稳定笼状结构，同时不作为离去基团。通过 X 射线晶体学和溶液 (19)F/(29)Si NMR 光谱分析 R(8)T(8)@F(-)，发现包封的氟八硅倍半氧烷笼具有非常相似的环境。研究了氟离子从笼内迁移到笼外而不破坏 T(8)骨架的情况，以及在硅倍半氧烷笼内包封其他阴离子的可能性。
