• Delcey, M.G.; Lindblad, R.; Timm, M.; Bülow, C.; Zamudio-Bayer, V.; von Issendorff, B.; Lau, J. T.; Lundberg, M.: Soft X-ray signatures of cationic manganese-oxo systems, including a high-spin manganese(v) complex. Physical Chemistry Chemical Physics 24 (2022), p. 3598-3610

10.1039/d1cp03667j
Open Access Version

Abstract:
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.