Artificial Mn4Ca Clusters with Exchangeable Solvent Molecules Mimicking the Oxygen‐Evolving Center in Photosynthesis

The natural Mn₄Ca cluster in photosystem II serves as a blueprint to develop artificial water‐splitting catalysts for the generation of solar fuel in artificial photosynthesis. Although significant advances have recently been achieved, it remains a great challenge to prepare robust artificial Mn₄Ca clusters that precisely mimic the structure and function of the biological catalyst. Herein, we report the isolation and structural characterization of two Mn₄CaO₄ complexes with polar solvent molecules, acetonitrile or N,N‐dimethylformamide, which closely mimics the two water molecules on the calcium ion, as well as the oxidation states of the four manganese ions and the main geometric structure of the natural Mn₄Ca cluster. These new artificial Mn₄Ca complexes provide important chemical clues to understand the structure and mechanism of the biological system.     

Biomimetic Hydrogenation Catalyzed by a Manganese Model of [Fe]-Hydrogenase

[Fe]-hydrogenase is an efficient biological hydrogenation catalyst. Despite intense research, Fe complexes mimicking the active site of [Fe]-hydrogenase have not achieved turnovers in hydrogenation reactions. Herein, we describe the design and development of a manganese(I) mimic of [Fe]-hydrogenase. This complex exhibits the highest activity and broadest scope in catalytic hydrogenation among known mimics. Thanks to its biomimetic nature, the complex exhibits unique activity in the hydrogenation of compounds analogous to methenyl-H₄MPT⁺, the natural substrate of [Fe]-hydrogenase. This activity enables asymmetric relay hydrogenation of benzoxazinones and benzoxazines, involving the hydrogenation of a chiral hydride transfer agent using our catalyst coupled to Lewis acid-catalyzed hydride transfer from this agent to the substrates.