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

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-l...

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Bibliographic Details
Main Authors: Lohmeyer, Lukas (Author) , Schön, Florian (Author) , Kaifer, Elisabeth (Author) , Himmel, Hans-Jörg (Author)
Format: Article (Journal)
Language:English
Published: 2021
In: Angewandte Chemie. International edition
Year: 2021, Volume: 60, Issue: 18, Pages: 10415-10422
ISSN:1521-3773
DOI:10.1002/anie.202101423
Online Access:Verlag, kostenfrei, Volltext: https://doi.org/10.1002/anie.202101423
Verlag, kostenfrei, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202101423
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Author Notes:Lukas Lohmeyer, Florian Schön, Elisabeth Kaifer, and Hans-Jörg Himmel
Description
Summary: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.
Item Description:Gesehen am 17.04.2023
Physical Description:Online Resource
ISSN:1521-3773
DOI:10.1002/anie.202101423

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