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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
Author(s) -
Schrempp David Fridolin,
Kaifer Elisabeth,
Wadepohl Hubert,
Himmel HansJörg
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201602402
Subject(s) - chemistry , ligand (biochemistry) , redox , non innocent ligand , solvent , copper , diamagnetism , valence (chemistry) , tautomer , crystallography , photochemistry , inorganic chemistry , stereochemistry , organic chemistry , receptor , biochemistry , physics , quantum mechanics , magnetic field
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 Cu II complex with neutral ligand unit or a Cu I complex with radical monocationic ligand unit is the adequate description. Under special conditions, a temperature‐dependent equilibrium of the two valence tautomeric forms (Cu II /neutral ligand and Cu I /radical monocationic ligand) is achieved. Removal of a ligand‐centered electron from a paramagnetic Cu II complex with a neutral ligand unit leads to a diamagnetic Cu I complex with a dicationic ligand unit through a redox‐induced electron‐transfer (RIET) process.