Phosphine-Catalyzed Si−C Coupling of Bissilylmethanes: Preparation of Cyclic (Cl<sub>2</sub>SiCH<sub>2</sub>)<sub>2</sub> and Linear Cl<sub>2</sub>Si(CH<sub>2</sub>SiCl<sub>3</sub>)<sub>2</sub> via Silylene and Silene Intermediates
作者:Soon Hyun Hong、Sang Il Hyun、Il Nam Jung、Won-Sik Han、Min-Hye Kim、Hoseop Yun、Suk-Woo Nam、Sang Ook Kang
DOI:10.1021/om901071k
日期:2010.2.8
Cyclic and linear carbosilanes, (Cl2SiCH2)2 (2) and Cl2Si(CH2SiCl3)2 (3), were produced from phosphine-catalized Si−C coupling reactions of bissilylmethanes, HCl2SiCH2SiX1X2Cl (X1, X2 = Cl (1), X1 = H, X2 = Cl (7), and X1 = Me, X2 = Cl (8)). The formation of compounds 2 and 3 suggested competing reaction pathways, involving dichlorosilene [CH2═SiCl2] and dichlorosilylene [:SiCl2] intermediates. Each intermediate
环状和线型碳硅烷(Cl 2 SiCH 2)2(2)和Cl 2 Si(CH 2 SiCl 3)2(3)是由双甲硅烷基甲烷的HCl阳离子化的Si-C偶联反应,HCl 2 SiCH 2 SiX 1制成的X 2 Cl(X 1,X 2 = Cl(1),X 1 = H,X 2 = Cl(7)和X 1 = Me,X 2 = Cl(8))。化合物的形成2种3表明竞争反应途径,涉及dichlorosilene [CH 2 ═SiCl 2 ]和dichlorosilylene [:的SiCl 2 ]的中间体。每种中间体要么通过三聚产物(3)的产物分离来提出,要么通过用2,3-二甲基丁二烯和二氯甲烷进行的捕集实验进行确认。