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A copper(I) complex with two unpaired electrons, synthesised by oxidation of a copper(II) complex with two redox-active ligands

Two homoleptic copper(II) complexes [Cu(L1)2] and [Cu(L2)2] with anionic redox-active ligands were synthesised, one with urea azine (L1) and the other with thio-urea azine (L2) ligands. One-electron oxidation of the complexes initiates an unprecedented redox-induced electron transfer process, leadin...

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Bibliographic Details
Main Authors: Werr, Marco (Author) , Kaifer, Elisabeth (Author) , Enders, Markus (Author) , Asyuda, Andika (Author) , Zharnikov, Michael (Author) , Himmel, Hans-Jörg (Author)
Format: Article (Journal)
Language:English
Published: 2021
In: Angewandte Chemie. International edition
Year: 2021, Volume: 60, Issue: 43, Pages: 23451-23462
ISSN:1521-3773
DOI:10.1002/anie.202109367
Online Access:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1002/anie.202109367
Verlag, lizenzpflichtig, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202109367
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Author Notes:Marco Werr, Elisabeth Kaifer, Markus Enders, Andika Asyuda, Michael Zharnikov, and Hans-Jörg Himmel
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Summary:Two homoleptic copper(II) complexes [Cu(L1)2] and [Cu(L2)2] with anionic redox-active ligands were synthesised, one with urea azine (L1) and the other with thio-urea azine (L2) ligands. One-electron oxidation of the complexes initiates an unprecedented redox-induced electron transfer process, leading to monocationic copper(I) complexes [Cu(L1)2]+ and [Cu(L2)2]+ with two oxidised ligands. While [Cu(L1)2]+ is best described as a CuI complex with two neutral radical ligands that couple antiferromagnetically, [Cu(L2)2]+ is a CuI complex with two clearly different ligand units in the solid state and with a magnetic susceptibility close to a diamagnetic compound. Further one-electron oxidation of the complex with L1 ligands results in a dication [Cu(L1)2]2+, best described as a CuI complex with a twofold oxidised, monocationic ligand and a neutral radical ligand. The stability in at least three redox states, the accumulation of spin density at the ligands and the facile ligand-metal electron transfer make these complexes highly attractive for a variety of applications; here the catalytic aerobic oxidation of alcohols to aldehydes is tested.
Item Description:First published: 23 August 2021
Gesehen am 29.11.2022
Physical Description:Online Resource
ISSN:1521-3773
DOI:10.1002/anie.202109367

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