Cyclic and linear carbosilanes, (Cl 2 SiCH 2 ) 2 (2) and Cl 2 Si(CH 2 SiCl 3 ) 2 (3), were produced from phosphine-catalized Si-C coupling reactions of bissilylmethanes, HCl 2 SiCH 2 SiX 1 X 2 Cl (X 1 , X 2 = Cl (1), X 1 = H, X 2 = Cl (7), and X 1 = Me, X 2 = Cl (8)). The formation of compounds 2 and 3 suggested competing reaction pathways, involving dichlorosilene [CH 2 dSiCl 2 ] and dichlorosilylene [:SiCl 2 ] intermediates. Each intermediate was either proposed by the product isolation of the trimerized product (3) or confirmed by trapping experiments with 2,3-dimethylbutadiene and methylene chloride.
[Bu4P]+Cl−-catalyzed reactions of trichlorosilane and dichloromethylsilane with vinyltrichlorosilane gave 1,1,4,4-tetrachloro-2,5-bis(trichlorosilyl)-1,4-disilacyclohexane (1) and 1,1,4,4-tetrachloro-2,5-bis(methyldichlorosilyl)-1,4-disilacyclohexane (4), respectively.
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