Department of Chemistry, Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623, Berlin, Germany.
Department of Chemistry: Theoretical Chemistry, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C7, 10623, Berlin, Germany.
Angew Chem Int Ed Engl. 2017 Feb 6;56(7):1894-1897. doi: 10.1002/anie.201610498. Epub 2017 Jan 12.
The first isolable molecular silicon dicarbonate complex (bis-NHC)Si(CO ) 2 (bis-NHC=H C[{NC(H)=C(H)N(Dipp)}C:] , Dipp=2,6-iPr C H ) 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)SiO 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 CO under liberation of CO; its subsequent Lewis acid-base reaction with CO 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.
首例可分离的分子硅碳酸酯配合物（双 NHC）Si(CO ) 2（双 NHC=H C[{NC(H)=C(H)N(Dipp)}C:]，Dipp=2,6-iPr C H ）是通过二价硅原子稳定的硅酮（双 NHC）Si 1与二氧化碳的简便反应合成的。单体二氧化硅配合物（双 NHC）SiO 3 由双 NHC 配体支撑，被提出为关键中间体，其由 1 中的零价硅原子通过两摩尔当量的 CO 双重氧化生成，释放出 CO；其随后与 CO 的路易斯酸碱反应导致生成 2，其已通过单晶 X 射线衍射分析进行了充分表征。其电子结构、光谱数据和形成的热化学已通过量子化学进行了研究。
