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 HBBr₂·SMe_2. 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鲁棒性的碳硼分子簇。这些end赋使碳硼烷成为有价值的构件，适用于从功能材料到药物的各种应用。因此，碳硼烷的化学已经引起了极大的研究兴趣，并且在过去的几十年中已经取得了重大进展。但是，自2005年报道14个顶点的碳硼烷以来，许多合成具有14个以上顶点的碳硼烷的尝试均未成功。问题在于是否存在这些长期追捧的分子。我们在本文中描述15和16顶点closo的合成和结构表征-carboranes以及16-vertruruthenacarborane。这种成功依赖于向两个笼碳中引入甲硅烷基，稳定相应的Nido- carborane二价阴离子并促进与HBBr ₂ ·SMe _2的键合反应_。这项工作将为制备具有17个或更多顶点的碳硼烷提供一些启示_。，并为研究超级碳烷化学打开了大门。