Institut für Anorganische und Analytische Chemie, Goethe-Universität, Max-von-Laue-Straße 7, 60438, Frankfurt/Main, Germany.
Chemistry. 2018 Dec 3;24(67):17796-17801. doi: 10.1002/chem.201803921. Epub 2018 Nov 5.
A preparatively facile, highly selective synthesis of bifunctional monosilanes R SiHCl, RSiHCl and RSiH Cl is reported. By chlorination of R SiH and RSiH with concentrated HCl/ether solutions, the stepwise introduction of Si-Cl bonds is readily controlled by temperature and reaction time for a broad range of substrates. In a combined experimental and computational study, we establish a new mode of Si-H bond activation assisted by Lewis bases such as ethers, amines, phosphines, and chloride ions. Elucidation of the underlying reaction mechanisms shows that alcohol assistance through hydrogen-bond networks is equally efficient and selective. Remarkably, formation of alkoxysilanes or siloxanes is not observed under moderate reaction conditions.
我们报道了一种制备简单、高选择性的双官能单硅烷 RSiHCl、RSiHCl 和 RSiHCl 的合成方法。通过 RSiH 和 RSiH 与浓 HCl/乙醚溶液的氯化反应，可以通过温度和反应时间来控制 Si-Cl 键的逐步引入，从而实现广泛的底物的控制。在实验和计算相结合的研究中，我们建立了一种新的 Si-H 键活化模式，这种模式得到了醚、胺、膦和氯离子等路易斯碱的辅助。对反应机制的阐明表明，通过氢键网络的醇辅助同样高效且具有选择性。值得注意的是，在温和的反应条件下，不会观察到烷氧基硅烷或硅氧烷的形成。
