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Modulation of a μ-1,2-Peroxo Dicopper(II) Intermediate by Strong Interaction with Alkali Metal Ions
- Source :
- Journal of the American Chemical Society. 143:17751-17760
- Publication Year :
- 2021
- Publisher :
- American Chemical Society (ACS), 2021.
-
Abstract
- The properties of metal/dioxygen species, which are key intermediates in oxidation catalysis, can be modulated by interaction with redox-inactive Lewis acids, but structural information about these adducts is scarce. Here we demonstrate that even mildly Lewis acidic alkali metal ions, which are typically viewed as innocent "spectators", bind strongly to a reactive cis-peroxo dicopper(II) intermediate. Unprecedented structural insight has now been obtained from X-ray crystallographic characterization of the "bare" CuII2(μ-η1:η1-O2) motif and its Li+, Na+, and K+ complexes. UV-vis, Raman, and electrochemical studies show that the binding persists in MeCN solution, growing stronger in proportion to the cation's Lewis acidity. The affinity for Li+ is surprisingly high (∼70 × 104 M-1), leading to Li+ extraction from its crown ether complex. Computational analysis indicates that the alkali ions influence the entire Cu-OO-Cu core, modulating the degree of charge transfer from copper to dioxygen. This induces significant changes in the electronic, magnetic, and electrochemical signatures of the Cu2O2 species. These findings have far-reaching implications for analyses of transient metal/dioxygen intermediates, which are often studied in situ, and they may be relevant to many (bio)chemical oxidation processes when considering the widespread presence of alkali cations in synthetic and natural environments.
- Subjects :
- chemistry.chemical_classification
010405 organic chemistry
chemistry.chemical_element
General Chemistry
010402 general chemistry
Photochemistry
Electrochemistry
Alkali metal
01 natural sciences
Biochemistry
Copper
Catalysis
0104 chemical sciences
Adduct
Metal
Colloid and Surface Chemistry
chemistry
visual_art
visual_art.visual_art_medium
Lewis acids and bases
Crown ether
Subjects
Details
- ISSN :
- 15205126 and 00027863
- Volume :
- 143
- Database :
- OpenAIRE
- Journal :
- Journal of the American Chemical Society
- Accession number :
- edsair.doi.dedup.....ae91dc3219f4dc3a936c632cf14a2ee3