Activation of CS
<sub>2</sub>
and CO
<sub>2</sub>
by Silylium Cations
作者:Carsten Jenne、Marc C. Nierstenhöfer、Valentin Lessen
DOI:10.1002/chem.202005003
日期:2021.2.15
weakly coordinating [Me3NB12Cl11]− anion, undergoes, in the presence of excess silane, a series of unexpected consecutive reactions with the valence‐isoelectronic molecules CS2 and CO2. The final products of the reaction with CS2 are methane and the previously unknown [(Et3Si)3S]+ cation. To gain insight into the entire reaction cascade, numerous experiments with varying conditions were performed, intermediate
在过量硅烷存在下,由弱配位的[Me 3 NB 12 Cl 11 ] -阴离子稳定的氢化桥硅烷基阳离子[Et 3 Si-H-SiEt 3 ] +会发生一系列意想不到的连续反应,与价等电子分子CS 2和CO 2。与CS 2反应的最终产物是甲烷和先前未知的[(Et 3 Si)3 S] +阳离子。为了深入了解整个反应级联,进行了许多不同条件的实验,拦截了中间产物,并通过X射线晶体学确定了它们的结构。除了作为最终产物的[(Et 3 Si)3 S] +阳离子之外,[(Et 3 Si)2 SMe] +,[Et 3 SiS(H)Me] +和[Et 3 SiOC(H )的晶体结构获得)OSiEt 3 ] +。实验结果与支持气相和溶液中量子化学计算的结果相结合,可以更详细地了解反应级联。