Pyramidanes
Pyramidanes
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DOI：
10.1021/ja403173e
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发表时间：
2013-06-19
影响因子：
15
通讯作者：
Minyaev, Ruslan M.
中科院分区：
文献类型：
--
作者：
Lee, Vladimir Ya.;Ito, Yuki;Minyaev, Ruslan M.
皮拉米烷是一个难以捉摸但又非常理想的合成目标，由于其非经典结构和不同寻常的键特征而引起了合成化学家的极大关注。虽然在理论基础上得到了充分的研究，但母体全碳金字塔烷及其含有较重的14族元素的衍生物都没有被分离和表征。在这篇通讯中，我们报道了这类高应变多面体化合物的第一个稳定代表：锗和锡酰胺Ge[C-4(SiMe3)(4)]和Sn[C-4(SiMe3)(4)]的合成和结构解析。结合实验和计算分析证实了这些化合物的特殊结构和成键特征，表明这些衍生物是非经典中性化合物，离子性质贡献很大。
Pyramidane is an elusive but highly desirable target for synthetic chemists that has attracted a great deal of attention because of its nonclassical structure and unusual bonding features. Although well studied on theoretical grounds, neither the parent all-carbon pyramidane nor its derivatives containing heavier group 14 elements have ever been isolated and characterized. In this Communication, we report on the synthesis and structural elucidation of the first stable representatives of this class of highly strained polyhedral compounds: germa- and stannapyramidanes Ge[C-4(SiMe3)(4)] and Sn[C-4(SiMe3)(4)]. The peculiar structural and bonding features of these compounds are verified by combined experimental and computational analyses, showing these derivatives to be nonclassical neutral compounds with a very large contribution of ionic character.