Abstract

Rearrangements that change the connectivity of a carbon skeleton are often useful in synthesis, but it can be difficult to follow their mechanisms. Scanning probe microscopy can be used to manipulate a skeletal rearrangement at the single-molecule level, while monitoring the geometry of reactants, intermediates and final products with atomic resolution. We studied the reductive rearrangement of 1,1-dibromo alkenes to polyynes on a NaCl surface at 5 K, a reaction that resembles the Fritsch–Buttenberg–Wiechell rearrangement. Voltage pulses were used to cleave one C–Br bond, forming a radical, then to cleave the remaining C–Br bond, triggering the rearrangement. These experiments provide structural insight into the bromo-vinyl radical intermediates, showing that the C=C–Br unit is nonlinear. Long polyynes, up to the octayne Ph–(C≡C)8–Ph, have been prepared in this way. The control of skeletal rearrangements opens a new window on carbon-rich materials and extends the toolbox for molecular synthesis by atom manipulation.

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Acknowledgements

The research leading to these results received funding from ERC Advanced Grants CEMAS (agreement no. 291194) and CoSuN (320969), ERC Consolidator Grant AMSEL (682144) and EU project PAMS (610446). P.G. acknowledges receipt of Postdoc.Mobility fellowships from the Swiss National Science Foundation. Y.X. was supported by the EPSRC Centre for Doctoral Training in Synthesis for Biology and Medicine (EP/L015838/1) and by a University of Oxford Clarendon Fund Scholarship. The authors acknowledge use of the Oxford Advanced Research Computing (ARC) facility to carry out computational work (doi: 10.5281/zenodo.22558). The authors thank R.S. Paton and I. Gruebner for discussions on computational studies and A.L. Thompson for help with X-ray crystal structure refinements.

Author information

Author notes

    • Niko Pavliček

    Present address: ABB Corporate Research, Baden-Dättwil, Switzerland

Affiliations

  1. IBM Research – Zurich, Rüschlikon, Switzerland

    • Niko Pavliček
    • , Zsolt Majzik
    • , Gerhard Meyer
    •  & Leo Gross
  2. Department of Chemistry, Oxford University, Chemistry Research Laboratory, Oxford, UK

    • Przemyslaw Gawel
    • , Daniel R. Kohn
    • , Yaoyao Xiong
    •  & Harry L. Anderson

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Contributions

P.G. conceived the project. N.P., Z.M., G.M. and L.G. performed the STM/AFM experiments and analysis. P.G. and D.R.K. performed the organic synthesis. Y.X. measured and solved X-ray crystal structures. H.L.A. contributed to the design of the study. All authors analysed the results and contributed to the manuscript.

Competing interests

The authors declare no competing interests.

Corresponding authors

Correspondence to Przemyslaw Gawel or Harry L. Anderson or Leo Gross.

Supplementary information

  1. Supplementary information

    Supplementary details about the synthesis and analysis of dibromoolefins, crystallographic information and extensive information on computational studies and additional surface experiments

  2. Crystallographic data

    CIF for compound 6Br4; CCDC reference: 1567547

  3. Crystallographic data

    Structure factors for compound 6Br4; CCDC reference: 1567547

  4. Crystallographic data

    CIF for compound 7Br4; CCDC reference: 1567546

  5. Crystallographic data

    Structure factors for compound 7Br4; CCDC reference: 1567546

  6. Crystallographic data

    CIF for compound 8Br4; CCDC reference: 1567548

  7. Crystallographic data

    Structure factors for compound 8Br4; CCDC reference: 1567548

  8. Calculated Cartesian coordinates

    Cartesian coordinates of geometries for all calculated structures

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DOI

https://doi.org/10.1038/s41557-018-0067-y