Ligand Design for the Development of New Applications in Organometallic Chemistry

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The Emslie research program is focused on the development of unique ligands and ligand combinations to advance the fields of organometallic catalysis and Atomic Layer Deposition (ALD), and to generate new knowledge and understanding. Under this umbrella, the three research themes in this proposal are:***(1) Lewis-acid appended transition metal complexes for applications in cooperative catalysis, with a focus on transformations involving alkenes, CO and CO2,***(2) Highly rigid pincer ligands for the synthesis of thermally robust rare earth and actinide olefin polymerization catalysts, and alkane s-complexes relevant to C-H bond activation, and***(3) New organometallic precursors and reactivities for Atomic Layer Deposition (ALD) of metal films.***Each of the above topics combines fundamental/exploratory organometallic chemistry with at least one target application that has not yet been realized, and is of high current importance:***The Lewis acid-appended transition metal complexes in research area 1 offer new possibilities for the development of challenging catalytic transformations involving CO and CO2. These transformations are economically desirable, and in the case of CO2, they would also be environmentally beneficial.***The rare earth metal catalysts targeted in area 2 are designed to exhibit high thermal stability, as required for industrial application. Catalysts based on the rare earth metals exhibit unique and desirable polymerization capabilities, such as facile copolymerization of ethylene with styrene, cyclic olefins, and dienes, and ethylene co-polymerization with very high levels of a-olefin incorporation. However, industrial use of these catalysts has typically been prevented by low thermal stability.***The metal-alkane complexes to be prepared in research area 2 feature a metal center located in a rigidly defined hydrophobic pocket. These complexes will provide valuable chemical insight relevant to C-H activation of highly unreactive alkanes, contributing either directly or indirectly to the development of future alkane functionalization reactivity.***The organometallic ALD precursors that are the focus of the research in area 3 are designed to exhibit a unique combination of high volatility, high thermal stability, and high reactivity with selected organometallic reagents. As such, they are expected to allow the development of the first methods for ALD of highly electropositive metals, which will be required to enable continued miniaturization of the basic components of microprocessors and memory devices.**