title: Redox-induced reversible metal assembly through translocation and reversible ligand coupling in tetranuclear metal sandwich frameworks.
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.
authors.affiliation: Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka, 565-0871, Japan. tetsu@chem.eng.osaka-u.ac.jp
authors.forename: Tetsuro
authors.initials: T
authors.lastname: Murahashi
authors.forename: Katsunori
authors.initials: K
authors.lastname: Shirato
authors.forename: Azusa
authors.initials: A
authors.lastname: Fukushima
authors.forename: Kohei
authors.initials: K
authors.lastname: Takase
authors.forename: Tomoyoshi
authors.initials: T
authors.lastname: Suenobu
authors.forename: Shunichi
authors.initials: S
authors.lastname: Fukuzumi
authors.forename: Sensuke
authors.initials: S
authors.lastname: Ogoshi
authors.forename: Hideo
authors.initials: H
authors.lastname: Kurosawa
mesh_terms: D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry*
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D010165:Palladium