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. 2007 Jul;40(7):601-8.
doi: 10.1021/ar700008c. Epub 2007 Apr 26.

Mononuclear Cu-O2 complexes: geometries, spectroscopic properties, electronic structures, and reactivity

Christopher J Cramer  1 , William B Tolman
Affiliations

Mononuclear Cu-O2 complexes: geometries, spectroscopic properties, electronic structures, and reactivity

Christopher J Cramer et al. Acc Chem Res. 2007 Jul.

Abstract

Using interwoven experimental and theoretical methods, detailed studies of several structurally defined 1:1 Cu-O 2 complexes have provided important fundamental chemical information useful for understanding the nature of intermediates involved in aerobic oxidations in synthetic and enzymatic copper-mediated catalysis. In particular, these studies have shed new light on the factors that influence the mode of O 2 coordination (end-on vs side-on) and the electronic structure, which can vary between Cu(II)-superoxo and Cu(III)-peroxo extremes.

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Figures

Figure 1
Figure 1
1:1 Cu/O2 complexes, of which all except 1b and 3a have been structurally defined by X-ray crystallography.
Figure 2
Figure 2
Cores of 1:1 Cu/O2 adducts determined by X-ray crystallography, with atoms as arbitrary spheres (1a) or 50% thermal ellipsoids (2 and 4) and selected bond distances (Å) and angles (deg) indicated. Atom color scheme: Cu, green; N, blue; O, red.
Figure 3
Figure 3
Plot of O-O distance (Å) vs. 1/ν2/3 (cm2/3) for a range of side-on MO2 complexes and H2O2, O2-, O2, and O2+. Experimental and calculated data are shown as blue circles and black squares, respectively, and are listed in Table S1. The data for complexes 1a, 2, 3b, and 4 are labeled, with a parenthetical “t” denoting values calculated via theory. The line is a fit to eq. 1 (see text).
Figure 4
Figure 4
Normalized Cu XAS data showing the ∼2 eV difference between the L3-edge transition energies for 1b and the Cu(II) complex [(TMPA)Cu(OH2)]2+ vs. those for 3b and the Cu(III) compound La2Li1/2Cu1/2O4. Adapted from ref. .
Figure 5
Figure 5
Calculated frontier molecular orbitals for the simplified (b-diketiminate)CuO2 complex shown, with a plot of Cu-O (red) and O-O (blue) distances as a function of the charge on the N-donor atoms. Adapted from ref. .
Figure 6
Figure 6
Calculated structure of the CuO2 adduct with a thioether-modified b-diketiminate ligand (selected interatomic distances shown; colors: blue, N; red, O; green, Cu; yellow. S).
Scheme 1
Scheme 1
Scheme 2
Scheme 2
Proposed dual pathway mechanism for the oxygenation yielding 3a.
Scheme 3
Scheme 3
Summary of the reactivity of 3a. S-H = phenols, thioanisole, cyclohexene, ferrocene, HBF4. pzH = 3,5-diphenylpyrazole. PR3 = PPh3 or PMePh2. TMS = trimethylsilyl. L = tetramethylpropanediamine, 1,4,7-trimethylcyclononane, or a β-diketiminate with orthomethylsubstituents.
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