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Redox-induced reversible metal assembly through translocation and reversible ligand coupling in tetranuclear metal sandwich frameworks

Nature Chemistry volume 4, pages 52–58 (2012)Cite this article

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An Erratum to this article was published on 15 December 2011

This article has been updated

Abstract

Sandwich structures formed by metal atoms intercalated between sp2-carbon planes can be found either in metal–graphite-based materials or discrete multinuclear sandwich complexes. Their reactivity, and in particular their dynamic behaviour, has recently attracted interest both from a structural and a practical aspect, for example in catalysis. However, progress in this area has been rather slow, and it remains difficult to elucidate their structure and behaviour at the molecular level. Here, we report two sandwich complexes—in which four palladium centres are incorporated between two π-conjugated ligands—which exhibit two modes of redox-switchable structural changes. In the first complex, the tetrapalladium chain is split by oxidation into two well-separated dipalladium units. This motion is reversed on reduction. In the second complex, reversible carbon–carbon coupling occurs between the ligands during the redox process.

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Figure 1: Dynamic behaviour of metal atoms or ions on a multidentate ligand.
Figure 2: Redox-induced dynamic behaviour of tetranuclear metal sandwich complexes.
Figure 3: Redox-induced reversible metal assembly in a tetranuclear metal sandwich framework.
Figure 4: Cyclic voltammograms of the tetranuclear Pd compounds involved in a redox-induced reversible metal assembly through translocation.
Figure 5: Redox-induced reversible C–C coupling of ligands in a tetranuclear metal sandwich framework.

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Change history

  • 21 November 2011

    In the version of this Article originally published online, an extraneous Pd atom appeared in Fig. 3. This has now been corrected in all versions of the Article.

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Acknowledgements

Part of this work was supported by PRESTO, the Japan Science and Technology Agency (JST), the Ministry of Education, Science, Sports and Technology, Japan, and The Sumitomo Foundation.

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Authors and Affiliations

  1. Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka, 565-0871, Japan

    Tetsuro Murahashi, Katsunori Shirato, Azusa Fukushima, Kohei Takase, Sensuke Ogoshi & Hideo Kurosawa

  2. PRESTO, Japan Science and Technology Agency (JST),

    Tetsuro Murahashi

  3. Department of Material and Life Science, Graduate School of Engineering, Osaka University, Osaka, 565-0871, Japan

    Tomoyoshi Suenobu & Shunichi Fukuzumi

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Contributions

The idea and plans for this research were developed by T.M. Experiments were performed by T.M., K.S., A.F., K.T. and T.S. The data were analysed by T.M., K.S., A.F., K.T. and T.S. The manuscript was written by T.M. All authors discussed the results.

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Correspondence to Tetsuro Murahashi.

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Crystallographic data for compound 1'-OMe (CIF 71 kb)

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Murahashi, T., Shirato, K., Fukushima, A. et al. Redox-induced reversible metal assembly through translocation and reversible ligand coupling in tetranuclear metal sandwich frameworks. Nature Chem 4, 52–58 (2012). https://doi.org/10.1038/nchem.1202

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