B(C<sub>6</sub>
F<sub>5</sub>
)<sub>3</sub>
-Catalyzed Selective Chlorination of Hydrosilanes
作者:Karina Chulsky、Roman Dobrovetsky
DOI:10.1002/anie.201700324
日期:2017.4.18
were selectively chlorinated in the presence of a catalytic amount of B(C6F5)3 or Et2O⋅B(C6F5)3 and HCl with the release of H2 as a by‐product. The hydrides in di‐ and trihydrosilanes could be selectively chlorinated by HCl in a stepwise manner when Et2O⋅B(C6F5)3 was used as the catalyst. A mechanism is proposed for these catalytic chlorination reactions on the basis of competition experiments and density
Si-H键的氯化通常需要化学计量的金属盐以及有害试剂,例如氯化锡,Cl 2和CCl 4。硅烷的催化氯化通常涉及使用昂贵的过渡金属催化剂。通过一种新颖,简单,高效的无催化金属氢化方法,可在催化量的B(C 6 F 5)存在下对一,二和三氢硅烷进行氯化。3或Et 2 O⋅B(C 6 ˚F 5)3和HCl与H的释放2作为副产品。当将Et 2 O·B(C 6 F 5)3用作催化剂时,二氢硅烷和三氢硅烷中的氢化物可以通过HCl逐步进行氯化。在竞争实验和密度泛函理论(DFT)计算的基础上,提出了用于这些催化氯化反应的机理。