School of Chemistry, Raymond and Beverly Sackler Faculty of Exact Sciences, Tel Aviv University, Tel Aviv, 69978, Israel.
Angew Chem Int Ed Engl. 2017 Apr 18;56(17):4744-4748. doi: 10.1002/anie.201700324. Epub 2017 Mar 21.
The chlorination of Si-H bonds often requires stoichiometric amounts of metal salts in conjunction with hazardous reagents, such as tin chlorides, Cl , and CCl . The catalytic chlorination of silanes often involves the use of expensive transition-metal catalysts. By a new simple, selective, and highly efficient catalytic metal-free method for the chlorination of Si-H bonds, mono-, di-, and trihydrosilanes were selectively chlorinated in the presence of a catalytic amount of B(C F ) or Et O⋅B(C F ) and HCl with the release of H as a by-product. The hydrides in di- and trihydrosilanes could be selectively chlorinated by HCl in a stepwise manner when Et O⋅B(C F ) was used as the catalyst. A mechanism is proposed for these catalytic chlorination reactions on the basis of competition experiments and density functional theory (DFT) calculations.
硅氢键的氯化通常需要化学计量的金属盐与危险试剂（如氯化锡、Cl 和 CCl ）一起使用。硅烷的催化氯化通常涉及使用昂贵的过渡金属催化剂。通过一种新的简单、选择性和高效的无金属催化方法，可以在催化量的 B(C 6 F 5 ) 或 EtO⋅B(C 6 F 5 ) 和 HCl 的存在下，选择性地氯化单、二和三硅烷，同时释放出 H 作为副产物。当使用 EtO⋅B(C 6 F 5 ) 作为催化剂时，二硅烷和三硅烷中的氢化物可以通过 HCl 逐步选择性地氯化。根据竞争实验和密度泛函理论（DFT）计算，提出了这些催化氯化反应的机理。
