New type of green catalysts for aerobic oxidation of alcohols
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The ultimate goal of this research project is to develop highly active, robust and recyclable catalysts that use oxygen or air for oxidation of alcohols to aldehydes and ketones. We plan to exploit a number of complexes of MOF-immobilized strong field ligands with early transition metals for this purpose. In other words, we will prepare MOF-immobilized versions of the homogeneous catalysts for alcohol oxidation. Homogeneous catalysts are usually the most active catalyst for most transformations, because they can be optimized both sterically and electronically relatively easily. However, homogeneous catalysts are hard to recycle, which somewhat limits their industrial and medicinal application. So, tethering homogeneous catalysts to recyclable platforms while conserving their activity is likely to generate very interesting catalyst systems. We believe that this approach will enable us to develop highly active and recyclable catalysts due to two-fold benefit that MOF platforms are anticipated to provide: 1) MOFs have received a tremendous interest from research community and preparation of MOFs with a wide range of functionalities, topologies and particle sizes have been studied. This will enable us to prepare the materials with immobilized ligands possessing desirable characteristics such as chemical, mechanical, thermal stability, pore and particle size; and 2) MOFs have a highly regular and crystalline structure which allows for a precise control of the coordination environment around the transition metal. This feature allows for the immobilized systems to display very high activities and selectivities. Another important objective of this proposal is to provide research training to the undergraduate students engaged in this project. Although the undergraduate students listed for the project do have limited research exposure as they have been working in the LPIs lab on voluntary basis over the past few months, it is imperative to propose the research work that is commensurate to the experience of these undergraduate researchers. As such, we would like to note that the MOF-immobilized ligands that we propose below have been previously prepared for different applications in our research group and can easily be synthesized following simple and reproducible methods. Proposed MOF-immobilized complexes will also be air and moisture stable as proposed reactions will be carried out under oxidizing conditions in the presence of protic alcohol reagents.