CAS: Accessing and Tuning the Reactivity of Late-Metal Oxo and Nitrido Complexes Using Iminoxolene Supporting Ligands

点击翻译按钮获取中文摘要

With support from the Chemical Catalysis (CAT) Program in NSF's Division of Chemistry, Professor Seth Brown of the University of Notre Dame is designing new kinds of catalysts to speed up important chemical reactions. The particular catalysts of interest promise to contribute to the US economy by enhancing the efficiency of chemical manufacturing. The project is focusing on metal-containing catalysts with attention to both the identity of the metal and the metal environment. Knowledge of the metal-environment interactions will guide the design of improved catalysts that will react with oxygen gas to produce commodity chemicals. This grant also supports the professional training of the graduate, undergraduate, and high school students who are conducting research under the supervision of Professor Brown. Educational materials suitable for high school or beginning college students are being developed in order to enhance scientific education on a larger scale. With support from the Chemical Catalysis (CAT) Program in NSF's Division of Chemistry, Professor Seth Brown of the University of Notre Dame is developing new oxidation catalysts. Oxidation reactions mediated by catalysts of the late transition metals are important in nature as well as in the chemical industry. Terminal oxo compounds are often invoked as reactive intermediates, but few well-characterized examples are known. Specifically, Professor Brown is exploring the ability of ancillary ligands that strongly perturb the electronic structure of the metals to allow access to, or modify the properties of, terminal oxo and nitrido groups bonded to late transition metals. Synthetic, spectroscopic, and computational studies are carried out on such complexes to clarify the nature of the metal-ligand interactions and how these interactions modify the properties of the metal-oxo linkage. These studies are complemented by detailed mechanistic studies of reactions such as alkane hydroxylation or dehydrogenation to elucidate design rules. These insights contribute to the design and implementation of new oxidation catalysts with enhanced reactivity or selectivity. This project supports the professional development of the graduate, undergraduate, and high school students in Professor Brown's research group, affording them the technical and intellectual skills that help them become successful in the scientific workforce. Educational materials centering on chemical kinetics, which underpins the study of catalysis, at an advanced high school/introductory college level are being developed and made broadly available.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.