Technische Universität Berlin, Institute of Chemistry, Metalorganic and Inorganic Materials, Sekr. C2, Strasse des 17. Juni 135, 10623 Berlin, Germany.
Chemistry. 2011 Sep 26;17(40):11274-9. doi: 10.1002/chem.201101610. Epub 2011 Aug 25.
The first donor-stabilized silylated silicoxonium species LSi=O-SiMe(3) (L=(RN)C(=CH(2))CH=CMe(NR), R=2,6-iPr(2)C(6)H(3)) have been synthesized from the reaction of the dmap-supported (dmap=p-dimethylaminopyridine) silanone complex [LSi(dmap)=O] (1) with trimethylsilyl halides. Although the reaction with Me(3)SiCl leads directly to the Si=O addition product [LSi(Cl)OSiMe(3)] (2), the ionic silicoxonium bromide L(dmap)Si=O-SiMe(3)Br(-) (3) can be obtained as a primary product of the reaction with Me(3)SiBr, which affords [LSi(Br)OSiMe(3)] (4) with release of the dmap ligand at room temperature in THF. In the case of Me(3)SiI, the reaction furnishes the silicoxonium iodide L(dmap)Si=O-SiMe(3)I(-) (5) as the most stable species. Compounds 2-5 were isolated and fully characterized through multinuclear NMR spectroscopy, mass spectrometry, elemental analyses, and single-crystal X-ray diffraction analyses.
已从 dmap 支持的（dmap = p-二甲基氨基吡啶）硅酮配合物 [LSi（dmap）= O]（1）与三甲基卤化硅的反应中合成了第一 donor-stabilized silylated silicoxonium 物种 [LSi= O-SiMe（3）]（+）（L =（RN）C（= CH（2））CH = CMe（NR），R = 2,6-iPr（2）C（6）H（3））。尽管与 Me（3）SiCl 的反应直接导致 Si = O 加成产物 [LSi（Cl）OSiMe（3）]（2），但可以将离子硅氧烷溴化物 [L（dmap）Si = O-SiMe（3）]（+）Br（-）（3）作为与 Me（3）SiBr 反应的主要产物获得，该反应在室温下在 THF 中释放出 dmap 配体得到 [LSi（Br）OSiMe（3）]（4）。对于 Me（3）SiI，反应生成最稳定的物种硅氧烷碘化物 [L（dmap）Si = O-SiMe（3）]（+）I（-）（5）。化合物 2-5 通过多核 NMR 光谱，质谱，元素分析和单晶 X 射线衍射分析进行了分离和全面表征。
