An Isolable Silicon Dicarbonate Complex from Carbon Dioxide Activation with a Silylone
An Isolable Silicon Dicarbonate Complex from Carbon Dioxide Activation with a Silylone
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DOI：
10.1002/anie.201610498
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发表时间：
2017-02-06
影响因子：
16.6
通讯作者：
Driess, Matthias
中科院分区：
文献类型：
--
作者：
Burchert, Alexander;Yao, Shenglai;Driess, Matthias
通过双氮杂环卡宾稳定的含零价硅原子的硅酮（bis-NHC）Si 1与二氧化碳的简单反应，合成了第一个可分离的分子硅双炔配合物（bis-NHC）Si（CO 3）（2）2（bis-NHC= H2 C [{NC（H）=C（H）N（Dipp）}C：]（2），Dipp= 2，6-iPr（2）C（6）H（3））.的单体二氧化硅配合物（双-NHC）SiO2 3支持的双-NHC配体提出作为一个关键的中间体产生的双氧化的零价硅原子在1由两个摩尔当量的CO2下释放的CO;其随后的刘易斯酸碱反应与CO2导致2已被充分表征，包括单晶X-射线衍射分析。用量子化学方法研究了它的电子结构、光谱数据和形成过程的热化学。
The first isolable molecular silicon dicarbonate complex (bis-NHC)Si(CO3)(2) 2 (bis-NHC=H2C[{NC(H)=C(H)N(Dipp)}C:](2), Dipp=2,6-iPr(2)C(6)H(3)) was synthesized by facile reaction of the bis-N-heterocyclic carbene stabilized silylone (bis-NHC)Si 1, bearing a zero-valent silicon atom, with carbon dioxide. The monomeric silicon dioxide complex (bis-NHC)SiO2 3 supported by the bis-NHC ligand was proposed as a key intermediate resulting from double oxygenation of the zero-valent silicon atom in 1 by two molar equivalents of CO2 under liberation of CO; its subsequent Lewis acid-base reaction with CO2 leads to 2 which has been fully characterized including an single-crystal X-ray diffraction analysis. Its electronic structure, spectroscopic data and the thermochemistry of the formation have been studied quantum-chemically.