Theoretical characterization of end-on and side-on peroxide coordination in ligated Cu ₂O ₂ models

The relative energetics of μ-η ¹:η ¹ (trans end-on) and μ-η ²:η ² (side-on) peroxo isomers of Cu ₂O ₂ fragments supported by 0, 2, 4, and 6 ammonia ligands have been computed with various density functional, coupled-cluster, and multiconfigurational protocols. There is substantial disagreement between the different levels for most cases, although completely renormalized coupled-cluster methods appear to offer the most reliable predictions. The significant biradical character of the end-on peroxo isomer proves problematic for the density functionals, while the demands on active space size and the need to account for interactions between different states in second-order perturbation theory prove challenging for the multireference treatments. In the latter case, it proved impossible to achieve any convincing convergence.