Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai, 980-8578, Japan.
Chemistry. 2018 May 28;24(30):7774-7780. doi: 10.1002/chem.201801286. Epub 2018 May 9.
Activation of H by compounds of main-group elements has received considerable attention. Herein, we report synthesis of novel monoboryl- and monoamino-substituted disilenes and their characterization by a combination of NMR spectroscopy and single-crystal X-ray diffraction analysis. The monoboryldisilene reacts with two molecules of H to provide the corresponding trihydridodisilane and hydroborane, whereas the aminodisilene does not react with H under the same conditions. The present results together with our previous results indicate that the presence of the boryl-substituent on the Si=Si double bond is essential to activate the H molecule. The low lying empty 2p orbital on the boron atom that interacts effectively with the π*(Si=Si) orbital could be responsible for the activation of H .
主族元素化合物对 H 的活化受到了相当多的关注。在此，我们报告了新型单硼代和单氨基取代二硅烯的合成，并通过 NMR 光谱和单晶 X 射线衍射分析对其进行了表征。单硼代二硅烯与两个 H 分子反应，提供相应的三氢代二硅烷和氢硼烷，而氨基二硅烯在相同条件下不与 H 反应。目前的结果与我们之前的结果表明，Si=Si 双键上硼取代基的存在对于活化 H 分子是必不可少的。硼原子上低占据的空 2p 轨道与π*(Si=Si)轨道有效相互作用，可能是活化 H 的原因。
