Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, China.
Nat Commun. 2020 Nov 23;11(1):5943. doi: 10.1038/s41467-020-19661-5.
Carboranes are a class of carbon-boron molecular clusters with three-dimensional aromaticity, and inherent robustness. These endowments enable carboranes as valuable building blocks for applications ranging from functional materials to pharmaceuticals. Thus, the chemistry of carboranes has received tremendous research interest, and significant progress has been made in the past decades. However, many attempts to the synthesis of carboranes with more than 14 vertices had been unsuccessful since the report of a 14-vertex carborane in 2005. The question arises as to whether these long sought-after molecules exist. We describe in this article the synthesis and structural characterization of 15- and 16-vertex closo-carboranes as well as 16-vertex ruthenacarborane. Such a success relies on the introduction of silyl groups to both cage carbons, stabilizing the corresponding nido-carborane dianions and promoting the capitation reaction with HBBr·SMe This work would shed some light on the preparation of carboranes with 17 vertices or more, and open the door for studying supercarborane chemistry.
碳硼烷是一类具有三维芳香性和固有稳定性的硼碳分子簇。这些特性使碳硼烷成为从功能材料到药物等应用的有价值的构建块。因此，碳硼烷化学引起了极大的研究兴趣，在过去几十年中取得了重大进展。然而，自 2005 年报道了一个 14 顶点的碳硼烷以来，许多尝试合成超过 14 个顶点的碳硼烷的尝试都没有成功。人们不禁要问，这些长期以来备受追捧的分子是否存在。我们在本文中描述了 15 个和 16 个顶点的闭式碳硼烷以及 16 个顶点的钌碳硼烷的合成和结构表征。这样的成功依赖于在笼碳原子上引入硅基，稳定相应的 nido-碳硼烷二阴离子，并促进与 HBBr·SMe 的帽化反应。这项工作将为制备 17 个或更多顶点的碳硼烷提供一些启示，并为研究超碳硼烷化学打开大门。
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