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- W2892279980 abstract "A (μ-hydroxido, μ-phenoxido)CuIICuII complex 1 has been synthesized using an unsymmetrical ligand bearing an N,N-bis(2-pyridyl)methylamine (BPA) moiety coordinating one copper and a dianionic bis-amide moiety coordinating the other copper(II) ion. Electrochemical mono-oxidation of the complex in DMF occurs reversibly at 213 K at E1/2 = 0.12 V vs Fc+/Fc through a metal-centered process. The resulting species (complex 1+) is only stable at low temperature and has been spectroscopically characterized by UV–vis–NIR cryo-spectroelectrochemical and EPR methods. DFT and TD-DFT calculations, consistent with experimental data, support the formation of a CuIICuIII phenoxido-hydroxido complex. Low-temperature chemical oxidation of 1 by NOSbF6 yields a tetranuclear complex 2(SbF6)(NO2) which displays two binuclear CuIICuII subunits. The X-ray crystal structure of 2(SbF6)(NO2) evidences that the nitrogen of the terminal amide group is protonated and the coordination of the amide occurs via the O atom. The bis-amide moiety appears to be a non-innocent proton acceptor along the redox process. Alternatively, protonation of complex 1 leads to the complex 2(ClO4)2, as evidenced by X-ray crystallography, cyclic voltammetry, and 1H NMR." @default.
- W2892279980 created "2018-09-27" @default.
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- W2892279980 date "2018-09-18" @default.
- W2892279980 modified "2023-10-17" @default.
- W2892279980 title "Effect of Monoelectronic Oxidation of an Unsymmetrical Phenoxido-Hydroxido Bridged Dicopper(II) Complex" @default.
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- W2892279980 doi "https://doi.org/10.1021/acs.inorgchem.8b02127" @default.
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