Stimulation of redox-induced electron transfer by interligand hydrogen bonding in a cobalt complex with redox-active guanidine ligand

• Verfasst von: Lohmeyer, Lukas [VerfasserIn]
• Verfasst von: Schön, Florian [VerfasserIn]
• Verfasst von: Kaifer, Elisabeth [VerfasserIn]
• Verfasst von: Himmel, Hans-Jörg [VerfasserIn]
• Titel: Stimulation of redox-induced electron transfer by interligand hydrogen bonding in a cobalt complex with redox-active guanidine ligand
• Verf.angabe: Lukas Lohmeyer, Florian Schön, Elisabeth Kaifer, and Hans-Jörg Himmel
• Jahr: 2021
• Umfang: 8 S.
• Fussnoten: Gesehen am 17.04.2023
• Titel Quelle: Enthalten in: Angewandte Chemie. International edition
• Ort Quelle: Weinheim : Wiley-VCH, 1998
• Jahr Quelle: 2021
• Band/Heft Quelle: 60(2021), 18, Seite 10415-10422
• ISSN Quelle: 1521-3773
• DOI: doi:10.1002/anie.202101423
• Datenträger: Online-Ressource
• Sprache: eng
• Bibliogr. Hinweis: Parallele Sprachausgabe : deutschLohmeyer, Lukas, 1993 - : Stimulierung eines redoxinduzierten Elektronentransfers durch Interligand-Wasserstoffbrücken in einem Cobaltkomplex mit redoxaktivem Guanidin-Liganden
• Sach-SW: cobalt
• Sach-SW: electron transfer
• Sach-SW: guanidine
• Sach-SW: hydrogen bonding
• Sach-SW: redox active ligand
• K10plus-PPN: 1842949012
• K10plus-PPN:
  Universitätsbibliothek
• Lokale URL UB: Zum Volltext

Abstract

Octahedrally coordinated cobalt(II) complexes with a redox-active bisguanidine ligand and acac co-ligands were synthesized and their redox chemistry analysed in detail. The N−H functions in a bisguanidine ligand with partially alkylated guanidino groups form N−H⋅⋅⋅O hydrogen bonds with the acac co-ligands, thereby massively influencing the redox chemistry. For all complexes, the first one-electron oxidation is metal-centred, leading to CoIII complexes with neutral bisguanidine ligand units. Further one-electron oxidation is ligand-centred in the case of Co-bisguanidine complexes with fully alkylated guanidino groups, giving CoIII complexes with radical monocationic bisguanidine ligands. On the other hand, the hydrogen-bond strengthening upon oxidation of the Co-bisguanidine complex with partially alkylated guanidino groups initiates metal reduction (CoIII→CoII) and two-electron oxidation of the guanidine ligand, providing the first example for the stimulation of redox-induced electron transfer by interligand hydrogen bonding.