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

Tetsuro Murahashi, Katsunori Shirato, Azusa Fukushima, Kohei Takase, Tomoyoshi Suenobu, Shunichi Fukuzumi, Sensuke Ogoshi, Hideo Kurosawa

Research output: Contribution to journalArticlepeer-review

52 Scopus citations

Abstract

Sandwich structures formed by metal atoms intercalated between sp 2 -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.

Original languageEnglish
Pages (from-to)52-58
Number of pages7
JournalNature Chemistry
Volume4
Issue number1
DOIs
StatePublished - Jan 2012

Bibliographical note

Funding Information:
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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