Imagawa Taiki, Giarrana Luisa, Andrada Diego M, Morgenstern Bernd, Nakamoto Masaaki, Scheschkewitz David
Krupp-Chair for General and Inorganic Chemistry, Saarland University, 66123 Saarbrücken, Germany.
Graduate School of Advanced Science and Engineering, Hiroshima University, 739-8526 Higashi-Hiroshima, Japan.
J Am Chem Soc. 2023 Mar 1;145(8):4757-4764. doi: 10.1021/jacs.2c13530. Epub 2023 Feb 14.
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 shielded Si NMR resonance at -448.3 ppm for the apex silicon atom. Treatment with Fe(CO) results in the formation of the corresponding silapyramidane-iron complex. Silapyramidane also reacts with the cyclobutadiene starting material to cleanly afford a fluorescent spirobis(silole).
从四（三甲基硅基）环丁二烯和Roesky型脒基支持的硅烯出发，通过一系列加成和还原反应，经由一个具有环外Si═C键的可分离环丁烯中间体，顺利得到难以捉摸的硅金字塔烷。该硅金字塔烷的顶端硅原子在硅核磁共振谱中呈现出异常屏蔽的共振信号，化学位移为-448.3 ppm。用Fe(CO)处理会导致形成相应的硅金字塔烷-铁配合物。硅金字塔烷还与环丁二烯起始原料反应，顺利得到一种荧光螺双（硅杂环戊二烯）。
