Stable Silapyramidanes
Stable Silapyramidanes
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DOI：
10.1021/jacs.2c13530
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发表时间：
2023-02-14
影响因子：
15
通讯作者：
Scheschkewitz，David
中科院分区：
文献类型：
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作者：
Imagawa，Taiki;Giarrana，Luisa;Scheschkewitz，David
从四（三甲基甲硅烷基）环丁二烯和 Roesky 型脒基负载的亚甲硅基开始，一系列加成和还原通过具有环外 Si=C 键的可分离环丁烯中间体干净地得到难以捉摸的硅吡脒。硅吡啶烷的顶端硅原子在-448.3 ppm处具有异常屏蔽的29 Si NMR共振。用 Fe2(CO)9 处理会形成相应的硅吡啶-铁络合物。硅吡啶还与环丁二烯起始材料反应，干净地提供荧光螺双(silole)。
Starting from tetrakis(trimethylsilyl)cyclobutadiene and an amidinate-supported silylene of the Roesky-type, a sequence of addition and reduction cleanly gives the elusive silapyramidane via an isolable cyclobutene intermediate with an exocyclic Si═C bond. The silapyramidane features an unusually shielded29Si NMR resonance at −448.3 ppm for the apex silicon atom. Treatment with Fe2(CO)9results in the formation of the corresponding silapyramidane–iron complex. Silapyramidane also reacts with the cyclobutadiene starting material to cleanly afford a fluorescent spirobis(silole).