Intramolecular metal-ligand electron transfer triggered by co-ligand substitution

The possibility of directed stimulation of intramolecular electron transfer between a metal and a redox-active ligand in a molecular coordination compound is the key to its application in molecular catalysis and other research themes. Although the stimulation by a substitution reaction of the co-lig...

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Hauptverfasser: Ziesak, Alexandra Sabrina (VerfasserIn) , Steuer, Lena (VerfasserIn) , Kaifer, Elisabeth (VerfasserIn) , Wadepohl, Hubert (VerfasserIn) , Himmel, Hans-Jörg (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: 21 Jun 2018
In: Dalton transactions
Year: 2018, Jahrgang: 47, Heft: 28, Pages: 9430-9441
ISSN:1477-9234
DOI:10.1039/C8DT01234B
Online-Zugang:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1039/C8DT01234B
Verlag, lizenzpflichtig, Volltext: https://pubs.rsc.org/en/content/articlelanding/2018/dt/c8dt01234b
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Verfasserangaben:Alexandra Ziesak, Lena Steuer, Elisabeth Kaifer, Norbert Wagner, Johannes Beck, Hubert Wadepohl and Hans-Jörg Himmel

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520 |a The possibility of directed stimulation of intramolecular electron transfer between a metal and a redox-active ligand in a molecular coordination compound is the key to its application in molecular catalysis and other research themes. Although the stimulation by a substitution reaction of the co-ligands is often postulated as key step in catalytic cycles using redox-active ligands as electron reservoirs, there are only a few explicit examples for such reactions. Herein we report the synthesis of the first dicationic and dinuclear CuI complexes featuring the oxidized form of a redox-active tetrakisguanidine ligand (1,2,4,5-tetrakis(tetramethylguanidino)benzene 1) as a bridging ligand and two neutral co-ligands L (acetonitrile or pyridine), [1{Cu(Cl)L}2]2+. An intramolecular electron transfer between the copper atom and the tetrakisguanidine ligand 1, leading to a dinuclear CuII complex with the reduced form of the tetrakisguanidine ligand 1, is triggered by substitution of the neutral co-ligands L. 
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