Reaction of phenyl(trimethylsilyl)silylene with chloromethanes; Insertion into C-Cl bond and abstraction of chlorine and HCl

Article abstract of DOI:10.1016/0022-328X(90)85076-B

Photolysis of tris(trimethylsilyl)phenylsilane in chloromethanes, ClnCX(4-n), (n = 1-4, X = H, alkyl, and Cl) produced phenyl(trimethylsilyl)silylene as a major intermediate, which afforded three types of products: 1,1-dichloro-1-phenyltrimethyldisilane via abstraction of two chlorine atoms, 1-alkyl-1-chloro-1-phenyltrimethyl-disilane via insertion into the C-Cl bond, and 1-chloro-1-phenyl-2,2,2-trimethyldisilane via abstraction of HCl.Possible reaction mechanisms for the formation of these products were discussed based on initial formation of an 1,2-zwitterionic intermediate.A small amount of a radical-reaction product, 2-chloro-2-phenyl-hexamethyltrisilane, and a product considered to be a cyclohexadienyl derivative were detected in all cases as minor products.