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A Tricopper(I) Complex Competent for O Atom Transfer, C-H Bond Activation, and Multiple O2 Activation Steps
Brian J Cook1, Gianna N Di Francesco1, Matthew T Kieber-Emmons2
1Center for Catalysis and Florida Center for Heterocyclic Compounds, Department of Chemistry , University of Florida , Gainesville , Florida 32611-7200 , United States.
Inorganic Chemistry
|May 24, 2018
Summary
Tricopper(I) cyclophanate activates oxygen to form reactive intermediates capable of C-H bond activation. This study reveals a multicopper oxidase-like mechanism involving peroxo and di(oxo) species.
Area of Science:
- Inorganic Chemistry
- Organometallic Chemistry
- Catalysis
Background:
- Copper complexes are known to mimic the activity of multicopper oxidases.
- Understanding oxygen activation mechanisms is crucial for developing new catalytic processes.
Purpose of the Study:
- To investigate the oxygenation of a tricopper(I) cyclophanate complex.
- To elucidate the mechanism of C-H bond activation and O atom transfer mediated by this complex.
Main Methods:
- Nuclear Magnetic Resonance (1H NMR)
- Gas Chromatography/Mass Spectrometry (GC/MS)
- Electrospray Ionization Mass Spectrometry (ESI/MS)
- Stopped-flow UV/Visible spectroscopy
- Electron Paramagnetic Resonance (EPR)
- Density Functional Theory (DFT) calculations
Main Results:
- Oxygenation of the tricopper(I) cyclophanate yields reactive intermediates.
- Low product yields (<1%) observed for C-H activation, attributed to ligand oxidation.
- Transient peroxo- and di(μ-oxo)-bridged intermediates were identified.
- DFT calculations support a concerted proton-coupled electron transfer and radical rebound mechanism for C-H activation.
Conclusions:
- The tricopper(I) cyclophanate complex activates O2 via a multicopper oxidase-like pathway.
- The mechanism involves transient peroxo and di(μ-oxo) species, similar to native copper enzymes.
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