Redox-induced reversible metal assembly through translocation and reversible ligand coupling in tetr

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. Despite their potential roles in catalysis and materials science, the redox-induced dynamic structural changes in (sp2-carbon ligand)–(multiple metals)–(sp2-carbon ligand) systems are not well understood. Now, tetra-palladium sandwich complexes have been described that exhibit redox-switchable assembly of the metal centres or coupling of the ligands.

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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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