SILYLENE CHEMISTRY .I. THERMOLYSIS OF METHOXYPOLYSILANES

Kinetic, mass spectral, and chemical evidence is presented for the formation of divalent silicon (silylene) species in the thermolysis of methoxypolysilane derivatives. In the absence of alternative “trapping” agents, the silylenes insert into the silicon-oxygen bond of the parent methoxypolysilane. These silylenes could be intercepted by a variety of acetylenes to give 1,4-disilacyclohexadienes. This reaction appears to involve a rather specific dimerization of silacyclopropene intermediates. The silylenes could also be intercepted by butadienes to give silacyclopent-3-enes. The silylenes could not be intercepted by simple olefins such as tetramethylethylene. © 1968, American Chemical Society. All rights reserved.