Intramolecular C-H and C-F Bond Oxygenation by Site-Differentiated Tetranuclear Manganese Models of the OEC.

ABSTRACT: The dangler manganese center in the oxygen-evolving complex (OEC) of photosystem II plays an important role in the oxidation of water to dioxygen. Inspired by the structure of the OEC, we synthesized a series of site-differentiated tetra-manganese clusters [LMn₃(PhPz)₃OMn][OTf]_x (2: x = 2; 3: x = 1) that features an apical manganese ion-distinct from the others-that is appended to a trinuclear manganese core through an μ₄-oxygen atom bridge. This cluster design was targeted to facilitate studies of high-valent Mn-oxo formation, which is a proposed step in the mechanism for water oxidation by the OEC. Terminal Mn-oxo species-supported by a multinuclear motif-were targeted by treating 2 and 3 with iodosobenzene. Akin to our previously reported iron

SUBMITTER: Carsch KM 

PROVIDER: S-EPMC5669799 | biostudies-literature | 2017 Aug

REPOSITORIES: biostudies-literature