Modeling the Peroxide/Superoxide Continuum in 1:1 Side-on Adducts of O₂ with Cu

Gherman, B. F.; Cramer, C. J.
Inorg. Chem. 2004, 43, 7281.

The character of singlet (C₃N₂H₅)CuO₂ ranges smoothly between copper(III)-peroxide and copper(II)-superoxide with variation of the electronic character of the supporting b-diketiminate ligand. Over the range of the variation, multireference second-order perturbation theory predicts the ¹A₁ singlet state always to be lower in energy than the lowest triplet state (³B₁). The multideterminantal character of the biradical-like superoxide mesomer causes density functional theory sometimes to fail badly in predicting the relative energies of these same states, although other properties, like geometry, are of good quality.

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