12- and 11-Migratory Insertion Reactions of Silylated Germylene Adducts

摘要

The reactions of the PMe adduct of the silylated germylene [(Me Si) Si] Ge: with GeCl ·dioxane were found to yield 1,1-migratory insertion products of GeCl into one or two Ge–Si bonds. In a related reaction, a germylene was inserted with tris(trimethylsilyl)silyl and vinyl substituents into a Ge–Cl bond of GeCl . This was followed by intramolecular trimethylsilyl chloride elimination to another cyclic germylene PMe adduct. The reaction of the GeCl mono-insertion product (Me Si) SiGe:GeCl Si(SiMe ) with Me SiC≡CH gave a mixture of alkyne mono- and diinsertion products. While the reaction of a divinylgermylene with GeCl ·dioxane only results in the exchange of the dioxane of GeCl against the divinylgermylene as base, the reaction of [(Me Si) Si] Ge: with one GeCl ·dioxane and three phenylacetylenes gives a trivinylated germane with a chlorogermylene attached to one of the vinyl units.