Theoretical Characterization of End-On and Side-On Peroxide Coordination in Ligated Cu₂O₂ Models

The relative energetics of μ-η:η¹ (trans end-on) and μ-η:η² (side-on) peroxo isomers of Cu₂O₂ 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.