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

• Verfasst von: Ziesak, Alexandra Sabrina [VerfasserIn]
• Verfasst von: Steuer, Lena [VerfasserIn]
• Verfasst von: Kaifer, Elisabeth [VerfasserIn]
• Verfasst von: Wadepohl, Hubert [VerfasserIn]
• Verfasst von: Himmel, Hans-Jörg [VerfasserIn]
• Titel: Intramolecular metal-ligand electron transfer triggered by co-ligand substitution
• Verf.angabe: Alexandra Ziesak, Lena Steuer, Elisabeth Kaifer, Norbert Wagner, Johannes Beck, Hubert Wadepohl and Hans-Jörg Himmel
• E-Jahr: 2018
• Jahr: 21 Jun 2018
• Umfang: 12 S.
• Fussnoten: Gesehen am 02.04.2020
• Titel Quelle: Enthalten in: Dalton transactions
• Ort Quelle: London : Soc., 1972
• Jahr Quelle: 2018
• Band/Heft Quelle: 47(2018), 28, Seite 9430-9441
• ISSN Quelle: 1477-9234
• DOI: doi:10.1039/C8DT01234B
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1693841770

Abstract

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.