1,2- and 1,1-Migratory Insertion Reactions of Silylated Germylene Adducts

Abstract

The reactions of the PMe₃ adduct of the silylated germylene [(Me₃Si)₃Si]₂Ge: with GeCl₂·dioxane were found to yield 1,1-migratory insertion products of GeCl₂ 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 GeCl₂. This was followed by intramolecular trimethylsilyl chloride elimination to another cyclic germylene PMe₃ adduct. The reaction of the GeCl₂ mono-insertion product (Me₃Si)₃SiGe:GeCl₂Si(SiMe₃)₃ with Me₃SiC≡CH gave a mixture of alkyne mono- and diinsertion products. While the reaction of a divinylgermylene with GeCl₂·dioxane only results in the exchange of the dioxane of GeCl₂ against the divinylgermylene as base, the reaction of [(Me₃Si)₃Si]₂Ge: with one GeCl₂·dioxane and three phenylacetylenes gives a trivinylated germane with a chlorogermylene attached to one of the vinyl units.