Université de Toulouse, UPS, and CNRS, LHFA UMR 5069, 118 route de Narbonne, 31062, Toulouse, France.
Université de Toulouse, UPS, and CNRS, ICT FR2599, 118 route de Narbonne, 31062, Toulouse, France.
Angew Chem Int Ed Engl. 2017 Aug 21;56(35):10481-10485. doi: 10.1002/anie.201705644. Epub 2017 Jul 24.
Silanones 2 substituted by bulky amino- and phosphonium ylide substituents have been synthesized and isolated in crystalline form. Thanks to the steric protection and the strong electron-donating ability of the substituents, silanones 2 are persistent and only slowly dimerizes at room temperature (t =0.5 or 5 h). Structural and theoretical analysis of 2 indicate a short Si=O bond (1.533 Å) and an enhanced polarization toward the O atom compared to Me Si=O owing to the strong π-electron donation from the phosphonium ylide substituent.
已合成并分离出取代基为大体积氨基和鏻叶立德的二硅烷酮 2，呈结晶状态。由于取代基的空间位阻和强给电子能力，二硅烷酮 2 具有持久性，仅在室温下缓慢二聚（t = 0.5 或 5 h）。2 的结构和理论分析表明，与 Me Si=O 相比，Si=O 键（1.533 Å）较短，并且由于磷叶立德取代基的强π-电子供体，O 原子的极化增强。
