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Metathesis of Ge=Ge double bonds

Nature Chemistry volume 13, pages 373–377 (2021)Cite this article

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Abstract

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 A2Ge=GeAB starting materials are thus converted to symmetrically substituted derivatives of the A2Ge=GeA2 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 (A2Ge=GeB-X-BGe=GeA2), heavier acyclic diene metathesis polymerization occurs, in analogy to the widespread acyclic diene metathesis (ADMET) polymerization in the carbon case, yielding a polydigermene.

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Fig. 1: Metathesis of digermenes.
Fig. 2: Molecular structures of E-5a, E-5b and Z-5b in the solid state.
Fig. 3: Trapping of germylenes 6a,b and equilibrium between digermenes E-5b and Z-5b in solution.
Fig. 4: Molecular structure of 11 in the solid state.

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Data availability

Crystallographic data for the structures in this Article have been deposited at the Cambridge Crystallographic Data Centre under deposition nos. CCDC 1948744 (3b), 1948745 (E-5a), 1948746 (E-5b),1948747 (Z-5b), 1995973 (10) and 1995974 (11). Copies of data can be obtained free of charge from www.ccdc.cam.ac.uk/structures/. All other data supporting the findings of this study are available within the Article and its Supplementary Information.

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Acknowledgements

We acknowledge Deutsche Forschungsgemeinschschaft (SCHE906/5-1) for funding. We thank B. Oberhausen, T. Klein and G. Kickelbick for assistance with DSC, thermogravimetric analysis and DLS measurements.

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Authors and Affiliations

  1. Krupp Chair of General and Inorganic Chemistry, Saarland University, Saarbrücken, Germany

    Lukas Klemmer, Anna-Lena Thömmes, Michael Zimmer, Volker Huch, Bernd Morgenstern & David Scheschkewitz

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  1. Lukas Klemmer
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Contributions

L.K. and D.S. conceived and designed the experiments. L.K. and A.-L.T. synthesized and characterized all compounds. M.Z. performed solid-state NMR experiments. V.H. and B.M. carried out single-crystal X-ray structure determinations. L.K. analysed the data. L.K. performed and analysed the DFT calculations. L.K. and D.S. co-wrote the manuscript. D.S. acquired funding.

Corresponding author

Correspondence to David Scheschkewitz.

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The authors declare no competing interests.

Additional information

Peer review information Nature Chemistry thanks the anonymous reviewers for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–78, Tables 1–11, Methods and Discussion.

Supplementary Data 1

Crystallographic data of compound 3b

Supplementary Data 2

Crystallographic data of compound E-5a

Supplementary Data 3

Crystallographic data of compound E-5b

Supplementary Data 4

Crystallographic data of compound Z-5b

Supplementary Data 5

Crystallographic data of compound 10

Supplementary Data 6

Crystallographic data of compound 11

Supplementary Data 1

XYZ-files of all DFT-optimized structures

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Klemmer, L., Thömmes, AL., Zimmer, M. et al. Metathesis of Ge=Ge double bonds. Nat. Chem. 13, 373–377 (2021). https://doi.org/10.1038/s41557-021-00639-9

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