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A Ferromagnetically Coupled ( S =1) Peroxodicopper(II) Complex
Author(s) -
Kindermann Nicole,
Bill Eckhard,
Dechert Sebastian,
Demeshko Serhiy,
Reijerse Edward J.,
Meyer Franc
Publication year - 2015
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.201409709
Subject(s) - electron paramagnetic resonance , copper , chemistry , crystallography , ferromagnetism , stereochemistry , nuclear magnetic resonance , organic chemistry , physics , quantum mechanics
Copper enzymes play important roles in the binding and activation of dioxygen in biological systems. Key copper/dioxygen intermediates have been identified and studied in synthetic analogues of the metalloprotein active sites, including the μ‐η 2 :η 2 ‐peroxodicopper(II) motif relevant to type III dicopper proteins. Herein, we report the synthesis and characterization of a bioinspired dicopper system that forms a stable μ‐η 1 :η 1 ‐peroxo complex whose Cu‐O‐O‐Cu torsion is constrained to around 90° by ligand design. This results in sizeable ferromagnetic coupling between the copper(II) ions, which is detected by magnetic measurements and HF‐EPR spectroscopy. The new dicopper peroxo system is the first with a triplet ground state, and it represents a snapshot of the initial stages of O 2 binding at type III dicopper sites.