Ligand Design for the Development of New Applications in Organometallic Chemistry

Emslie研究项目的重点是开发独特的配体和配体组合，以推进有机金属催化和原子层沉积（ALD）领域的发展，并产生新的知识和理解。在此框架下，本提案的三个研究主题是：***(1)用于协同催化的lewis酸附加过渡金属配合物，重点是涉及烯烃，CO和CO2的转化；***(2)用于合成热稳健的稀土和锕系烯烃聚合催化剂的高刚性钳形配体，以及与C-H键激活相关的烷烃s-配合物；***(3)金属薄膜原子层沉积（ALD）的新型有机金属前驱体及其反应性。***以上每个主题都将基础/探索性有机金属化学与至少一种尚未实现的目标应用相结合，并且具有很高的当前重要性：***研究领域1中的Lewis酸附加过渡金属配合物为涉及CO和CO2的具有挑战性的催化转化的发展提供了新的可能性。这些转变在经济上是可取的，在二氧化碳的情况下，它们也对环境有益。***区域2中的稀土金属催化剂具有高的热稳定性，可用于工业应用。基于稀土金属的催化剂表现出独特而理想的聚合能力，例如乙烯与苯乙烯、环烯烃和二烯的易共聚，以及乙烯与高水平的a-烯烃的共聚合。然而，这些催化剂的工业应用通常因热稳定性低而受阻。***在研究区域2中制备的金属-烷烃配合物的特征是金属中心位于严格定义的疏水口袋中。这些配合物将为高不活性烷烃的碳氢活化提供有价值的化学见解，直接或间接地为未来烷烃功能化反应性的发展做出贡献。***领域3研究重点的有机金属ALD前体被设计成具有高挥发性、高热稳定性和与选定的有机金属试剂的高反应性的独特组合。因此，它们有望允许开发高正电性金属ALD的第一种方法，这将需要实现微处理器和存储设备基本组件的持续小型化

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.**