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Activating catalysts with mechanical force

Nature Chemistry volume 1, pages 133–137 (2009)Cite this article

Abstract

Homogeneously catalysed reactions can be ‘switched on’ by activating latent catalysts. Usually, activation is brought about by heat or an external chemical agent. However, activation of homogeneous catalysts with a mechanical trigger has not been demonstrated. Here, we introduce a general method to activate latent catalysts by mechanically breaking bonds between a metal and one of its ligands. We have found that silver(i) complexes of polymer-functionalized N-heterocyclic carbenes, which are latent organocatalysts, catalyse a transesterification reaction when exposed to ultrasound in solution. Furthermore, ultrasonic activation of a ruthenium biscarbene complex with appended polymer chains results in catalysis of olefin metathesis reactions. In each case, the catalytic activity results from ligand dissociation, brought about by transfer of mechanical forces from the polymeric substituents to the coordination bond. Mechanochemical catalyst activation has potential applications in transduction and amplification of mechanical signals, and mechanically initiated polymerizations hold promise as a novel repair mechanism in self-healing materials.

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Figure 1: Concept, catalysts used and reactions of mechanical catalyst activation.
Figure 2: Mechanochemical activation of a catalytic ring-closing metathesis (RCM) reaction.
Figure 3: The fate of catalyst 6b after activation by ultrasound.
Figure 4: Experimental evidence for a dissociative mechanism of the mechanical activation of the ruthenium–benzylidene catalyst 6b.
Figure 5: Mechanochemical activation of a catalytic ring-opening metathesis polymerization (ROMP).

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Acknowledgements

This work was supported by grants from the Netherlands Organization for Scientific Research (NWO). We thank R.T.M. Jakobs for help with the synthesis of compounds 6 and 7.

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Authors and Affiliations

  1. Institute for Complex Molecular Systems, Eindhoven University of Technology, PO Box 513, Eindhoven, 5600, MB, The Netherlands

    Alessio Piermattei, S. Karthikeyan & Rint P. Sijbesma

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  1. Alessio Piermattei
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  2. S. Karthikeyan
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  3. Rint P. Sijbesma
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Contributions

R.P.S. conceived the sonochemical catalyst activation experiment and directed the research. A.P. and S.K. performed the experiments. All of the authors participated in writing the paper.

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Correspondence to Rint P. Sijbesma.

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Piermattei, A., Karthikeyan, S. & Sijbesma, R. Activating catalysts with mechanical force. Nature Chem 1, 133–137 (2009). https://doi.org/10.1038/nchem.167

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