Ligand Design for the Development of New Applications in Organometallic Chemistry

EMSLIE的研究计划专注于开发独特的配体和配体组合，以促进金属有机催化和原子层沉积(ALD)领域的发展，并产生新的知识和理解。在这一框架下，这项建议中的三个研究主题是：*(1)路易斯酸添加的过渡金属络合物在合作催化中的应用，重点是涉及烯烃、CO和CO2的转化；*(2)高刚性钳形配体用于合成耐热的稀土和榄系烯烃聚合催化剂，以及与C-H键活化有关的烷烃S络合物；以及*(3)用于原子层沉积的新的有机金属前驱体和反应活性。*上述主题中的每一个都结合了基础/探索性有机金属化学和至少一个尚未实现的目标应用，并具有很高的当前重要性：*研究区域1中的Lewis酸添加的过渡金属络合物为开发涉及CO和CO2的具有挑战性的催化转化提供了新的可能性。这些转变在经济上是可取的，在二氧化碳的情况下，它们也将有利于环境。*区域2中的稀土金属催化剂设计为表现出高热稳定性，符合工业应用的要求。基于稀土金属的催化剂表现出独特和理想的聚合性能，例如乙烯与苯乙烯、环烯烃和双烯的简单共聚，以及具有很高水平的α-烯烃的乙烯共聚。然而，这些催化剂的工业应用通常受到热稳定性较低的阻碍。*研究区域2将制备的金属-烷烃络合物的特点是金属中心位于严格定义的疏水口袋中。这些络合物将提供与高度非活性烷烃的C-H活化相关的有价值的化学见解，直接或间接地有助于未来烷烃官能化反应性的发展。*作为区域3研究的重点，有机金属ALD前驱体被设计为表现出高挥发性、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，预计它们将允许开发出第一批用于高电正性金属的ALD方法，这将是实现微处理器和存储设备基本组件的持续小型化所必需的。**

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.**