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Polymerization of silanes through dehydrogenative Si–Si bond formation on metal surfaces

Abstract

Element–element double bonds of group 14 elements can be formed in solution, but generally only by applying harsh reductive conditions using sterically highly shielded tetryl halides as precursors. The two-dimensional confinement in surface-assisted polymerization represents a valuable alternative to access such reactive compounds, as it allows shielding of the labile entities without requiring bulky residues and catalytic activation of the reactive groups. Here, we demonstrate Si–Si bond formation in on-surface chemistry. Polymerization upon multiple Si–H bond dissociation and subsequent Si–Si bond formation was achieved on Au(111) and Cu(111) surfaces by using two different monomers, each containing two silicon functional groups (CH3SiH2 or SiH3) attached to an aromatic backbone, leading to polymeric disilenes that interact with the surface. A combination of experimental and theoretical studies corroborates the formation of covalent Si–Si bonds between the long, highly ordered polymer chains with high diastereoselectivity. The reactive Si=Si bonds formally generated via double dehydrogenative coupling are stabilized via covalent Si–surface interaction.

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Fig. 1: General reaction scheme of the on-surface reactivity of biphenylsilanes on the Cu(111) and Au(111) surfaces.
Fig. 2: On-surface reaction of AMS 2 on the Au(111) surface.
Fig. 3: On-surface reaction of AMS 2 on the Cu(111) surface.
Fig. 4: XPS spectra of the Si 2p core levels of AMS deposited on the Cu(111) surface.
Fig. 5: On-surface reaction of BDS 3 on the Cu(111) surface.
Fig. 6: Energy profile of the proposed polymerization of model silane M on the Cu(111) surface.

Data availability

Supplementary Information is available in the online version of the paper. Reprints and permissions information is available online at www.nature.com/reprints. Data supporting the findings of this work are available within this paper or its Supplementary Information and also from all corresponding authors upon reasonable request. Converged adsorption geometries of all investigated structures can be found in a separate .zip file.

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Acknowledgements

We gratefully acknowledge financial support from the Deutsche Forschungsgemeinschaft (DFG) within the collaborative research centres SFB 858 (projects B02, Z01) and TRR61 (projects B03 and B07). H.M. and H.F. further thank the DFG for support through projects MO 2345/4-1 and FU 299/19. H.-Y.G. acknowledges financial support from NSFC within Grant 21972104 and ‘1000-Youth Talents Plan’. We thank D. Yesilpinar for technical support during the AFM measurements.

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L.L. performed the STM experiments. H. Kong participated in the STM experiments of BDS 3. H. Klaasen performed organic synthesis. M.C.W. performed theoretical studies. B.S.L., L.L. and A.T. performed XPS experiments and B.S.L. and L.L. performed the nc-AFM experiments, both experiments were supervised by H.M. All authors discussed the results. H.-Y.G., J.N., H.F. and A.S. supervised the project and designed the experiments. L.L., H. Klaasen, M.C.W., A.T., H.-Y.G. and A.S. wrote the manuscript with suggestions from all authors.

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Correspondence to Hong-Ying Gao, Johannes Neugebauer, Harald Fuchs or Armido Studer.

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Supplementary Information

Chemical synthesis, Supplementary Figs. 1–30, Tables 1–3, Discussion and NMR spectra of new compounds.

Supplementary Data

Zip-file containing the converged adsorption geometries of all investigated structures as .txt files.

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Liu, L., Klaasen, H., Witteler, M.C. et al. Polymerization of silanes through dehydrogenative Si–Si bond formation on metal surfaces. Nat. Chem. 13, 350–357 (2021). https://doi.org/10.1038/s41557-021-00651-z

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