Institute of Organic Chemistry, Justus-Liebig-University, Heinrich-Buff-Ring 58, 35392 Giessen (Germany).
Schulich Faculty of Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, 32000 Haifa (Israel).
Angew Chem Int Ed Engl. 2015 Oct 12;54(42):12404-9. doi: 10.1002/anie.201501844. Epub 2015 Aug 20.
We report the evaporation of a stable cyclic silylene and its oxidation (with ozone or N2 O) through oxygen atom transfer to form the corresponding silanone under matrix isolation conditions. As uncomplexed silanones are rare owing to their very high reactivity, this method provides an alternative route to these sought-after molecules. The silanone, as well as a novel bicyclic silane with a bridgehead silicon atom derived from an intramolecular silylene CH bond insertion, were characterized by comparison of high-resolution infrared spectra with density functional theory (DFT) computations at the M06-2X/cc-pVDZ level of theory.
我们报告了在基质隔离条件下，通过氧原子转移，稳定的环状硅烯的蒸发及其氧化（与臭氧或 N2 O），形成相应的硅酮。由于未配位的硅酮由于其非常高的反应性而很少见，因此这种方法为这些备受追捧的分子提供了另一种途径。硅酮以及一种具有桥原子的新型双环硅烷，是通过分子内硅烯 CH 键插入衍生而来的，通过与密度泛函理论（DFT）在 M06-2X/cc-pVDZ 理论水平上的计算进行高分辨率红外光谱的比较来进行表征。
