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Stimulation of Redox‐Induced Electron Transfer by Interligand Hydrogen Bonding in a Cobalt Complex with Redox‐Active Guanidine Ligand
Author(s) -
Lohmeyer Lukas,
Schön Florian,
Kaifer Elisabeth,
Himmel HansJörg
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202101423
Subject(s) - chemistry , redox , non innocent ligand , ligand (biochemistry) , cobalt , electron transfer , alkylation , metal , guanidine , hydrogen bond , photochemistry , medicinal chemistry , stereochemistry , inorganic chemistry , organic chemistry , molecule , catalysis , receptor , biochemistry
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 Co III 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 Co III 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 (Co III →Co II ) and two‐electron oxidation of the guanidine ligand, providing the first example for the stimulation of redox‐induced electron transfer by interligand hydrogen bonding.