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Intermolecular On-Surface σ-Bond Metathesis

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† Center for Nanotechnology, Heisenbergstraße 11, 48149 Münster, Germany
‡ Physikalisches Institut, Westfälische Wilhelms-Universität, Wilhelm-Klemm-Straße 10, 48149 Münster, Germany
∥ §Organisch-Chemisches Institut and ∥Center for Multiscale Theory and Computation, Westfälische Wilhelms-Universität, Corrensstraße 40, 48149 Münster, Germany
*[email protected] (H.-Y.G.)
*[email protected] (A.S.)
*[email protected] (H.F.)
Cite this: J. Am. Chem. Soc. 2017, 139, 20, 7012–7019
Publication Date (Web):May 3, 2017
https://doi.org/10.1021/jacs.7b02430
Copyright © 2017 American Chemical Society
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    Abstract

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    Silylation and desilylation are important functional group manipulations in solution-phase organic chemistry that are heavily used to protect/deprotect different functionalities. Herein, we disclose the first examples of the σ-bond metathesis of silylated alkynes with aromatic carboxylic acids on the Ag(111) and Au(111) surfaces to give the corresponding terminal alkynes and silyl esters, which is supported by density functional theory calculations and further confirmed by X-ray photoelectron spectroscopy analysis. Such a protecting group strategy applied to on-surface chemistry allows self-assembly structures to be generated from molecules that are inherently unstable in solution and in the solid state. This is shown by the successful formation of self-assembled hexaethynylbenzene at Ag(111). Furthermore, it is also shown that on the Au(111) surface this σ-bond metathesis can be combined with Glaser coupling to fabricate covalent polymers via a cascade process.

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