Difluorocarbene insertion into SiH bonds: the preparation and properties of difluoromethylsilanes
作者:H. Bürger、R. Eujen、P. Moritz
DOI:10.1016/0022-328x(91)86223-d
日期:1991.1
Difluorocarbene, CF2, generated by thermal decomposition of Cf3SiF3 at 100°C, has been found to insert into the SiH bonds of halosilanes SiH3X (X = F, Cl, Br, I), methylhalosilanes CH3SiH2X (X = Br, Cl) and (CH3)2SiHCl, and disiloxane (SiH3)2O. Use of excess of the CF2-source CF3SiF3 and of pressure favour the formation of the di-insertion products (CHF2)2SiHX and (CHF2)2(CH3)SiX. (CHF2)3SiCl was
发现Cf 3 SiF 3在100°C下热分解生成的二氟卡宾CF 2插入卤代硅烷SiH 3 X(X = F,Cl,Br,I),甲基卤代硅烷CH 3的SiH键中的SiH 2 X(X为Br,cl)和(CH 3)2的SiHCl,和二硅氧烷硅烷(SiH 3)2的过量的CF的使用O. 2 -source CF 3的SiF 3和的压力有利于二-的形成插入产品(CHF 2)2 SiHX和(CHF 2)2(CH 3)六。在CF 3 SiF 3和(CHF 2)SiH 2 Cl的共热解中形成的产物中鉴定出(CHF 2)3 SiCl 。相反,有机硅烷R n SiH 4- n(R = Me,Ph; n = 0-4),二卤代硅烷SiH 2 X 2和RSiHX 2,三卤代硅烷HSiX 3和四卤代硅烷SiX 4在这些条件下不与CF 2反应。根据空间和电子参数讨论了二氟卡宾的反应性和选择性。动力学氘效应已观察到k(SiH)/