RUI: Production of Highly Reactive Metal-Oxo Species with Molecular Oxygen and Visible Light for the Selective Oxidative Catalysis

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In this project funded by the Chemical Catalysis Program of the Chemistry Division, Professor Rui Zhang at the Western Kentucky University is designing efficient photocatalysts (catalysts that function with the input of light) that can utilize sunlight to activate oxygen and transfer it to other chemicals, also termed oxidation. The use of sunlight and atmospheric oxygen rather than a chemical reagent in the oxidation processes of bulk chemicals would be more sustainable, generate less chemical waste, and potentially reduce economic costs associated with the process. The research may impact the fundamental science and technology of green chemistry. The project is providing cutting-edge research experiences for the participating undergraduate STEM students and thereby training future STEM professionals. High school students from Gatton Academy are also spending time in the laboratory and learning about catalysis research.Dr. Zhang is studying ways to produce highly reactive metal(V)-oxo species in a catalytic cycle through photo-disproportionation of mu-oxo metal(IV) dimers. Initial studies in this research laboratory have demonstrated unique reactivity of ruthenium(IV) mu-oxo bisporphyrins and iron(IV) mu-oxo corroles in which high valent transition-metal oxo intermediates are accessed through the disproportionation. Now, Prof. Zhang is studying ways to produce the more reactive manganese(V)-oxo species via photo-disproportionation reactions and to develop efficient oxidations catalyzed by more stable metallocorrole complexes. Synthetic pathways are being developed to link a photosensitizer to the catalyst and to improve the light harvesting efficiency of the catalyst.