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（通常是高反应性分子），这可以提供对化学键合和反应性的新理解，并可以推进特定应用。这些应用包括用于制造新的有机分子和材料（包括聚合物）的催化反应、在微处理器和存储器设备制造期间存款目前无法获得的超薄膜的方法、以及用于将锕系金属与其它金属分离的化学技术。 在研究领域1中，我们将合成罕见的刚性金属键合 分子（配体）被设计为严格控制 用于特定目的的金属结合环境。这些配体将是 用于制备和研究极其罕见的稀有 稀土、锕系元素和4族烷基二价阳离子，它们都是高度 反应性和热鲁棒性，从而使他们的研究 结构和反应性，以及应用的发展 催化作用（如烯烃聚合和加氢）。 此外，它们将用于制备锕系元素络合物， 前所未有的锕系配体相互作用。对这些分子的研究 将有助于更好地理解锕系元素的成键 配合物，并可能指向改进方法的锕系元素 环境放射化学和锕系元素回收中的分离。 研究领域2专注于使用原子层沉积（ALD）进行薄膜沉积的高反应性分子（含有金属碳键的分子）的合成和应用。ALD可以说是唯一能够沉积超薄和高度保形（即表面拥抱）薄膜的技术，这将在未来的微处理器和存储器设备中需要，特别是当沉积需要在具有纳米级特征的表面上时，如深沟槽。然而，ALD中的膜生长依赖于分子之间的基于表面的反应，并且在许多情况下，还没有构想出合适的分子和反应。纯金属的热ALD特别具有挑战性，并且对于大多数早期和中期过渡金属尚未实现。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中，我们将致力于开发广泛适用的含金属分子的新路线，其特征在于与硅等元素具有多个键的配体。这项工作建立在几个最近的埃姆斯利集团出版物在锰的化学，并针对罕见的或前所未有的金属配体相互作用的根本利益。将研究所得含金属分子的结构、键合和反应性，并探讨其在催化反应（如烯烃氢化硅烷化）中的潜在参与。

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 actinideligand 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 metalcarbon 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 metalligand 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.