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- W2958746568 abstract "Abstract Copper(II)-hydroperoxo species are often detected as key intermediates in metalloenzymes and biomimetic compounds containing copper. However, the only reactivity has previously been observed for the copper(II)-hydroperoxo complexes is electrophilic, occurring through O-O bond cleavage. Here we report that a mononuclear end-on copper(II)-hydroperoxo complex, which has been successfully characterized by various physicochemical methods including UV-vis, rRaman, CSI-MS and EPR, is a reactive oxidant that utilizes a nucleophilic mechanism. In addition, DFT calculations fully support the electronic structure of this complex as a copper(II)-hydroperoxo complex with trigonal bipyramidal coordination geometry. A positive Hammett ρ value (2.0(3)) is observed in the reaction of copper(II)-hydroperoxo complex with para -substituted acyl chlorides, which clearly indicates nucleophilic character for the copper(II)-hydroperoxo complex. The copper(II)-hydroperoxo complex is an especially reactive oxidant in aldehyde deformylation with 2-PPA and CCA relative to the other metal-bound reactive oxygen species reported so far. The observation of nucleophilic reactivity for a copper(II)-hydroperoxo species expands the known chemistry of metal-reactive oxygen species." @default.
- W2958746568 created "2019-07-23" @default.
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- W2958746568 date "2019-07-18" @default.
- W2958746568 modified "2023-10-14" @default.
- W2958746568 title "Nucleophilic reactivity of a copper(II)-hydroperoxo complex" @default.
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- W2958746568 doi "https://doi.org/10.1038/s42004-019-0187-3" @default.
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