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- W2004308178 abstract "The effect of endogenous donor strength on Cu2O2 bonds was studied by electronically perturbing [{(R−TMPA)CuII}2(O2)]2+ and [{(R−MePY2)Cu}2(O2)]2+ (R = H, MeO, Me2N), which form the end-on μ-1,2 bound peroxide and an equilibrium mixture of side-on peroxo-dicopper(II) and bis-μ-oxo-dicopper(III) isomers, respectively. For [{(R-TMPA)CuII}2(O2)]2+, νO-O shifts from 827 to 822 to 812 cm-1 and νCu-O(sym) shifts from 561 to 557 to 551 cm-1, respectively, as R− varies from H to MeO to Me2N. Thus, increasing the N-donor strength to the copper decreases peroxide π*σ donation to the copper, weakening the Cu−O and O−O bonds. A decrease in νCu-O of the bis-μ-oxo-dicopper(III) complex was also observed with increasing N-donor strength for the R−MePY2 ligand system. However, no change was observed for νO-O of the side-on peroxo. This is attributed to a reduced charge donation from the peroxide π*σ orbital with increased N-donor strength, which increases the negative charge on the peroxide and adversely affects the back-bonding from the Cu to the peroxide σ* orbital. However, an increase in the bis-μ-oxo-dicopper(III) isomer relative to side-on peroxo-dicopper(II) species is observed for R−MePY2 with R = H < MeO < Me2N. This effect is attributed to the thermodynamic stabilization of the bis-μ-oxo-dicopper(III) isomer relative to the side-on peroxo-dicopper(II) isomer by strong donor ligands. Thus, the side-on peroxo-dicopper(II)/bis-μ-oxo-dicopper(III) equilibrium can be controlled by electronic as well as steric effects." @default.
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- W2004308178 date "2003-04-01" @default.
- W2004308178 modified "2023-10-03" @default.
- W2004308178 title "Resonance Raman Investigation of Equatorial Ligand Donor Effects on the Cu<sub>2</sub>O<sub>2</sub><sup>2+</sup> Core in End-On and Side-On μ-Peroxo-Dicopper(II) and Bis-μ-oxo-Dicopper(III) Complexes" @default.
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- W2004308178 doi "https://doi.org/10.1021/ja0276366" @default.
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