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. 2014 May 5;53(19):4935-9.
doi: 10.1002/anie.201402166. Epub 2014 Apr 2.

Observation of a Cu(II)(2) (μ-1,2-peroxo)/Cu(III)(2) (μ-oxo)(2) equilibrium and its implications for copper-dioxygen reactivity

Matthew T Kieber-Emmons  1 , Jake W Ginsbach, Patrick K Wick, Heather R Lucas, Matthew E Helton, Baldo Lucchese, Masatatsu Suzuki, Andreas D Zuberbühler, Kenneth D Karlin, Edward I Solomon
Affiliations

Observation of a Cu(II)(2) (μ-1,2-peroxo)/Cu(III)(2) (μ-oxo)(2) equilibrium and its implications for copper-dioxygen reactivity

Matthew T Kieber-Emmons et al. Angew Chem Int Ed Engl. .

Abstract

Synthesis of small-molecule Cu2 O2 adducts has provided insight into the related biological systems and their reactivity patterns including the interconversion of the Cu(II) 2 (μ-η(2) :η(2) -peroxo) and Cu(III) 2 (μ-oxo)2 isomers VSports手机版. In this study, absorption spectroscopy, kinetics, and resonance Raman data show that the oxygenated product of [(BQPA)Cu(I) ](+) initially yields an "end-on peroxo" species, that subsequently converts to the thermodynamically more stable "bis-μ-oxo" isomer (Keq =3. 2 at -90 °C). Calibration of density functional theory calculations to these experimental data suggest that the electrophilic reactivity previously ascribed to end-on peroxo species is in fact a result of an accessible bis-μ-oxo isomer, an electrophilic Cu2 O2 isomer in contrast to the nucleophilic reactivity of binuclear Cu(II) end-on peroxo species. This study is the first report of the interconversion of an end-on peroxo to bis-μ-oxo species in transition metal-dioxygen chemistry. .

Keywords: Raman spectroscopy; copper; dioxygen ligands; structure-function relationship; tyrosinase V体育安卓版. .

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Figures (V体育2025版)

Figure 1
Figure 1
Cu2O2 isomers.
Figure 2
Figure 2
Ligand scaffolds.
Figure 3
Figure 3
Time-dependent UV-vis spectra (207 s) for the oxygenation of [(BQPA)CuI]+ 1 in THF at –98.6 °C and absorbance–time traces at 380 nm and 550 nm (insert). Initially, the 370 nm band of 1 decays as the spectral features of 2 forms (—) followed by the decay of 2 and the growth of 3 (- -).
Figure 4
Figure 4
Resonance Raman spectra of 2, prepared with natural abundance O2 (—) and 18O2 (—) with 568 nm excitation in THF. Inset: Spectrum scaled 5X
Figure 5
Figure 5
Resonance Raman spectra of 3 prepared with natural abundance O2 (—) and 18O2 (—) with 380 nm excitation in THF.
Figure 6
Figure 6
End-on peroxo/Bis-μ-oxo isomerization.
Figure 7
Figure 7
Computational evaluation of electrophilic aromatic substitution by a end-on peroxo (—) and bis-μ-oxo (—) of 4.
Scheme 1
Scheme 1
Parallel kinetic model.
See this image and copyright information in PMC

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