Organosilicon Chemistry.

Several new aspects of the chemistry of silylenes, divalent reactive silicon intermediates, have been explored. Insertion reactions of dimethylsilylene into O-H bonds of primary, secondary, and tertiary alcohols were studied. This provides an efficient route to alkoxydimethylsilanes. It was found that solvent significantly affects the reactivity of dimethylsilylene in such insertion reactions. The insertion of dimethylsilylene into Si-O bonds of alkoxysilanes permits the synthesis of a novel series of cyclic polysilanes. New insertion reactions of dimethyldilylene into silicon-sulfur and sulfur-sulfur bonds were discovered. In the chemistry of siloxane oligomers it was found that secondary and tertiary alkyl lithium reagents will add to the carbon-carbon bond of vinyl di-or trisiloxanes at low temperatures to yeild alpha-lithio di-or trisiloxanes at low temperatures to yield alpha-lithio di-or trisiloxanes with no attack by the alkyl lithium reagent on the siloxane bond.