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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| Auteurs principaux: | , , , |
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| Format: | Article (Journal) |
| Langue: | anglais |
| Publié: |
2021
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| In: |
Angewandte Chemie. International edition
Year: 2021, Volume: 60, Numéro: 18, Pages: 10415-10422 |
| ISSN: | 1521-3773 |
| DOI: | 10.1002/anie.202101423 |
| Accès en ligne: | 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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| Notes sur l'auteur: | Lukas Lohmeyer, Florian Schön, Elisabeth Kaifer, and Hans-Jörg Himmel |
| Résumé: | 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. |
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| Description: | Gesehen am 17.04.2023 |
| Description matérielle: | Online Resource |
| ISSN: | 1521-3773 |
| DOI: | 10.1002/anie.202101423 |