Ligand Design for the Development of New Applications in Organometallic Chemistry

Emslie研究计划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，并产生新的知识和理解。在这一保护伞下，本提案中的三个研究主题是：*（1）路易斯酸附加的过渡金属络合物在协同催化中的应用，重点是涉及烯烃，CO和CO2的转化，*（2）用于合成热稳定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键活化相关的烷烃s-络合物，以及 *（3）用于金属膜原子层沉积（ALD）的新有机金属前体和反应性。上述每个主题都结合了基础/探索性有机金属化学与至少一个尚未实现的目标应用，并且具有很高的当前重要性：* 研究领域1中的刘易斯酸附加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。这些转化在经济上是可取的，就二氧化碳而言，它们也将对环境有益。区域2中的目标稀土金属催化剂被设计为表现出工业应用所需的高热稳定性。基于稀土金属的催化剂表现出独特和期望的聚合能力，例如乙烯与苯乙烯、环烯烃和二烯的容易的共聚，以及具有非常高水平的α-烯烃掺入的乙烯共聚。然而，这些催化剂的工业应用通常受到低热稳定性的阻碍。在研究区域2中制备的金属-烷烃络合物具有位于严格限定的疏水口袋中的金属中心。这些配合物将提供与高度不反应的烷烃的C-H活化相关的有价值的化学见解，直接或间接地促进未来烷烃官能化反应性的发展。有机金属ALD前体是领域3中研究的焦点，其设计表现出高挥发性、高热稳定性和与所选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用于高度正电性金属的ALD的第一种方法，这将是实现微处理器和存储设备的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.**