Steric control of dioxygen activation pathways for Mn^II complexes supported by pentadentate, amide-containing ligands.

ABSTRACT: Dioxygen activation at manganese centers is well known in nature, but synthetic manganese systems capable of utilizing O₂ as an oxidant are relatively uncommon. These present investigations probe the dioxygen activation pathways of two mononuclear Mn^II complexes supported by pentacoordinate amide-containing ligands, [Mn^II(dpaq)](OTf) and the sterically modified [Mn^II(dpaq^2Me)](OTf). Dioxygen titration experiments demonstrate that [Mn^II(dpaq)](OTf) reacts with O₂ to form [Mn^III(OH)(dpaq)](OTf) according to a 4 : 1 Mn : O₂ stoichiometry. This stoichiometry is consistent with a pathway involving comproportionation between a Mn^IV-oxo species and residual Mn^II complex to form

SUBMITTER: Parham JD 

PROVIDER: S-EPMC6733413 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature