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

Molecules. 2020 Feb 6;25(3):686. doi: 10.3390/molecules25030686.

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.

Keywords: 1,1-insertion; 1,2-insertion; germanium dichloride; germylene.

MeSH terms

  • Coordination Complexes / chemical synthesis*
  • Coordination Complexes / chemistry
  • Dioxanes / chemistry*
  • Molecular Structure
  • Phosphines / chemistry*
  • Silanes

Substances

  • Coordination Complexes
  • Dioxanes
  • Phosphines
  • Silanes
  • germylene
  • trimethyl phosphine
  • 1,4-dioxane