101. Photosystem II like water oxidation mechanism in a bioinspired tetranuclear manganese complex.
- Author
-
Liao RZ, Kärkäs MD, Lee BL, Åkermark B, and Siegbahn PE
- Subjects
- 2,2'-Dipyridyl chemistry, Biomimetic Materials chemical synthesis, Catalysis, Coordination Complexes chemical synthesis, Kinetics, Oxidants chemistry, Oxidation-Reduction, Photosystem II Protein Complex chemistry, Quantum Theory, Ruthenium Compounds chemistry, Thermodynamics, Biomimetic Materials chemistry, Coordination Complexes chemistry, Manganese chemistry, Oxygen chemistry, Water chemistry
- Abstract
The synthesis of Mn-based catalysts to mimic the structural and catalytic properties of the oxygen-evolving complex in photosystem II is a long-standing goal for researchers. An interesting result in this field came with the synthesis of a Mn complex that enables water oxidation driven by the mild single-electron oxidant [Ru(bpy)3](3+). On the basis of hybrid density functional calculations, we herein propose a water oxidation mechanism for this bioinspired Mn catalyst, where the crucial O-O bond formation proceeds from the formal Mn4(IV,IV,IV,V) state by direct coupling of a Mn(IV)-bound terminal oxyl radical and a di-Mn bridging oxo group, a mechanism quite similar to the presently leading suggestion for the natural system. Of importance here is that the designed ligand is shown to be redox-active and can therefore store redox equivalents during the catalytic transitions, thereby alleviating the redox processes at the Mn centers.
- Published
- 2015
- Full Text
- View/download PDF