Metathesis of Ge=Ge double bonds

The metathesis of carbon–carbon double bonds—the ‘reshuffling’ of their constituting carbene fragments—is a tremendously important preparative tool in industry and academia. Metathesis of heavier alkene homologues is restricted to occasional unproductive examples in phosphorus chemistry and cross-metathesis to mixed heavier alkynes. We now report the thermally induced, transition-metal-free metathesis of purpose-built unsymmetrically substituted digermenes. The A 2 Ge=GeAB starting materials are thus converted to symmetrically substituted derivatives of the A 2 Ge=GeA 2 and ABGe=GeAB types. The use of tethered auxiliary donors (dimethylaniline groups) in substituents B ensures intramolecular donor–acceptor stabilization of the transient germylene fragments, the intermediacy of which is proven by trapping experiments. Density functional theory calculations shed light on the thermodynamic driving force of the metathesis and validate the crucial role of the tethered donor. With an analogously equipped bridged tetragermadiene precursor (A 2 Ge=GeB-X-BGe=GeA 2 ), heavier acyclic diene metathesis polymerization occurs, in analogy to the widespread acyclic diene metathesis (ADMET) polymerization in the carbon case, yielding a polydigermene. The metathesis of carbon–carbon double bonds is an important tool in organic synthesis and now a similar reshuffling has been carried out with heavier alkene analogues featuring unsymmetrically substituted Ge=Ge double bonds. This reaction enables the synthesis of symmetric molecular digermenes as well as a polymer based on Ge=Ge repeat units.