Soft X-ray signatures of cationic manganese-oxo systems, including a high-spin manganese(v) complex

Manganese-oxo species catalyze key reactions, including C-H bond activation or dioxygen formation in natural photosynthesis. To better understand relevant reaction intermediates, we characterize electronic states and geometric structures of [MnOn]+ manganese-oxo complexes that represent a wide range of manganese oxidation states. To this end, we apply soft X-ray spectroscopy in a cryogenic ion trap, combined with multiconfigurational wavefunction calculations. We identify [MnO2]+ as a rare high-spin manganese(v) oxo complex with key similarities to six-coordinated manganese(v) oxo systems that are proposed as reaction intermediates in catalytic dioxygen bond formation.