Reactive Organometallic Complexes and Ligand Design for Catalysis, Actinide Complexation, and Thin Film Deposition

EMSLIE研究计划专注于设计和合成独特的含金属分子(通常是高活性分子)，这些分子可以提供对化学键和反应性的新理解，并可以促进特定应用。这些应用包括催化反应以制造包括聚合物在内的新的有机分子和材料，在微处理器和存储器件制造过程中沉积目前无法获得的超薄膜的方法，以及将鳗系金属与其他金属分离的化学技术。在研究领域1，我们将合成非同寻常的刚性金属结合分子(配体)，这些分子(配体)被设计成为特定目的严格控制金属结合环境。这些配体将被用来制备和研究具有高活性和热稳定性的极不常见的稀土、榄系元素和4族烷基化合物的结构，从而能够研究它们的结构和反应活性，并开发其在催化方面的应用(例如，烯烃聚合和氢化元素化)。此外，它们还将被用于制备具有前所未有的鳗系元素-配体相互作用的鳗系元素络合物。对这些分子的研究将有助于我们更好地理解鳗系元素络合物中的成键作用，并可能为环境放射化学和鳗系元素回收利用中的鳗系元素分离方法的改进指明方向。研究领域2的重点是利用原子层沉积技术(ALD)制备用于薄膜沉积的高活性分子(含金属-碳键的分子)及其应用。ALD可以说是唯一一种能够沉积超薄和高度共形(即表面拥抱)薄膜的技术，这将是未来微处理器和存储设备所需的，特别是当需要在具有纳米级特征的表面上沉积时，如深沟槽。然而，ALD中薄膜的生长依赖于分子之间的表面反应，在许多情况下，合适的分子和反应还没有构思出来。纯金属的热ALD特别具有挑战性，对于大多数早过渡金属和中期过渡金属来说，还没有实现这一点。在这项研究中，我们将开发独特的分子和反应，以实现目前无法获得的早期和中期过渡金属薄膜的ALD，这些薄膜是制造未来技术设备所需的。在研究领域3，我们将致力于开发广泛适用的含金属分子的新路线，这些分子的特点是与硅等元素有多个键的配体。这项工作建立在埃姆斯利集团最近在锰化学上发表的几篇论文的基础上，目标是稀有或前所未有的具有根本意义的金属-配体相互作用。我们将研究合成的含金属分子的结构、成键和反应活性，并探索它们在催化反应中的潜在作用，如烯烃硅氢加成反应。

The Emslie research program is focused on the design and synthesis of unique metal-containing molecules (typically highly reactive molecules) which can provide new understanding of chemical bonding and reactivity, and can advance specific applications. These applications include catalytic reactions to manufacture new organic molecules and materials including polymers, methods to deposit currently inaccessible ultra-thin films during microprocessor and memory device fabrication, and chemical techniques to separate actinide metals from other metals. In research area 1, we will synthesize uncommonly rigid metal-binding molecules (ligands) which have been designed to tightly control the metal binding environment for a specific purpose. These ligands will be used to prepare and study the structures of extremely uncommon rare earth, actinide and group 4 alkyl dications which are both highly reactive and thermally robust, thereby enabling the study of their structures and reactivity, and the development of applications in catalysis (e.g. alkene polymerization and hydroelementation). Furthermore, they will be used to prepare actinide complexes featuring unprecedented actinide-ligand interactions. Study of these molecules will provide a better understanding of the bonding in actinide complexes, and may point the way towards improved methods for actinide separation in environmental radiochemistry and actinide recycling. Research area 2 is focused on the synthesis and applications of highly reactive molecules (those containing metal-carbon linkages) for thin film deposition using Atomic Layer Deposition (ALD). ALD is arguably the only technique capable of depositing the ultra-thin and highly conformal (i.e. surface hugging) films which will be required in future microprocessors and memory devices, especially when deposition is required on surfaces with nano-scale features such as deep trenches. However, film growth in ALD relies upon surface-based reactions between molecules, and in many cases, suitable molecules and reactions have yet to be conceived. Thermal ALD of pure metals is particularly challenging, and has not been achieved for most early and mid transition metals. In this research, we will develop unique molecules and reactions to enable ALD of currently inaccessible early and mid transition metal thin films; those required to manufacture future technological devices. In research area 3, we will work towards the development of broadly-applicable new routes to metal-containing molecules which feature ligands with multiple bonds to elements such as silicon. This work builds upon several recent Emslie group publications in the chemistry of manganese, and targets rare or unprecedented metal-ligand interactions of fundamental interest. The structures, bonding, and reactivity of the resulting metal-containing molecules will be investigated, and their potential involvement in catalytic reactions, such as alkene hydrosilylation, will be explored.