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Copper complexes of new redox-active 4,5-bisguanidino-substituted benzodioxole ligands: control of the electronic structure by counter-ligands, solvent, and temperature

Herein, we analyze the possibility of controlling the electronic structure of mononuclear copper complexes featuring new redox-active 4,5-bisguanidino-substituted benzodioxole ligands. The nature of the guanidino groups, the anionic counter-ligands, the applied solvent (polarity), and the temperatur...

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Main Authors: Schrempp, David (Author) , Kaifer, Elisabeth (Author) , Wadepohl, Hubert (Author) , Himmel, Hans-Jörg (Author)
Format: Article (Journal)
Language:English
Published: September 28, 2016
In: Chemistry - a European journal
Year: 2016, Volume: 22, Issue: 45, Pages: 16187-16199
ISSN:1521-3765
DOI:10.1002/chem.201602402
Online Access:Resolving-System, lizenzpflichtig, Volltext: https://doi.org/10.1002/chem.201602402
Verlag, lizenzpflichtig, Volltext: https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/chem.201602402
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Author Notes:David Fridolin Schrempp, Elisabeth Kaifer, Hubert Wadepohl, and Hans-Jörg Himmel
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Summary:Herein, we analyze the possibility of controlling the electronic structure of mononuclear copper complexes featuring new redox-active 4,5-bisguanidino-substituted benzodioxole ligands. The nature of the guanidino groups, the anionic counter-ligands, the applied solvent (polarity), and the temperature are the parameters that decide if a CuII complex with neutral ligand unit or a CuI complex with radical monocationic ligand unit is the adequate description. Under special conditions, a temperature-dependent equilibrium of the two valence tautomeric forms (CuII/neutral ligand and CuI/radical monocationic ligand) is achieved. Removal of a ligand-centered electron from a paramagnetic CuII complex with a neutral ligand unit leads to a diamagnetic CuI complex with a dicationic ligand unit through a redox-induced electron-transfer (RIET) process.
Item Description:Gesehen am 22.05.2020
Physical Description:Online Resource
ISSN:1521-3765
DOI:10.1002/chem.201602402

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