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Nucleophilic reactivity of a copper(II)-hydroperoxo complex

Title
Nucleophilic reactivity of a copper(II)-hydroperoxo complex
Authors
Kim, BoheeJeong, DonghyunOhta, TakehiroCho, Jaeheung
DGIST Authors
Cho, Jaeheung
Issue Date
2019-07
Citation
Communications Chemistry, 2(1), 81
Type
Article
Article Type
Article
ISSN
2399-3669
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. © 2019, The Author(s).
URI
http://hdl.handle.net/20.500.11750/10446
DOI
10.1038/s42004-019-0187-3
Publisher
Nature Publishing Group
Related Researcher
  • Author Cho, Jaeheung Biomimetic Materials Laboratory
  • Research Interests Biomimetics; Metalloenzymes; Nitric Oxide Suppliers in Brain; Biomimetic Materials in Life
Files:
Collection:
Department of Emerging Materials ScienceBiomimetic Materials Laboratory1. Journal Articles


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