Metal-centred or ligand-based? Catholyte and anolyte redox reactions of actinyl(VI) complexes with open- and closed-shell 5f orbitals.

Using a N3O2-pentadentate chelating scaffold (saldien2-) decorated with tBu substituents for steric protection of its oxidized radical enables two chemically reversible redox reactions at both the metal centre and ligand side of actinyl(VI) (AnVIO22+) complexes, regardless of the absence (An = U) or presence (An = Pu) of 5f valence electrons.