An Isolable Tetrasilicon Analogue of a Planar Bicyclo[1.1.0]butane with π-Type Single-Bonding Character
An Isolable Tetrasilicon Analogue of a Planar Bicyclo[1.1.0]butane with π-Type Single-Bonding Character
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DOI：
10.1021/jacs.0c03874
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发表时间：
2020-06-03
影响因子：
15
通讯作者：
Iwamoto, Takeaki
中科院分区：
文献类型：
--
作者：
Nukazawa, Takumi;Iwamoto, Takeaki
含有π键而没有潜在的σ键框架（π型单键）的可分离化合物仍然很少。本文报道了1，3-二碘四硅双环[1.1.0]丁烷2的合成及其性质。2的单晶X射线衍射分析揭示了一个平面的双环硅环，其具有围绕桥头硅原子的平面几何形状和长的桥头Si-Si距离。DFT计算表明，2中的桥头Si原子之间存在π型单键，并表明2的高平面性最有可能归因于桥位置处的大体积取代基。
Isolable compounds that contain pi bonding without an underlying sigma-bond framework (pi-type single bonding) remain scarce. Herein we report the synthesis and properties of 1,3-diiodotetrasilabicyclo[1.1.0]butane 2 via 1,2-diiodination of the corresponding bridgehead disilene 1. Single-crystal X-ray diffraction analysis of 2 revealed a planar bicyclic silicon ring with a planar geometry around the bridgehead silicon atoms and a long bridgehead Si-Si distance. DFT calculations suggested a pi-type single bond between the bridgehead Si atoms in 2 and indicated that the high planarity of 2 should most likely be attributed to the bulky substituents at the bridge positions.