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

Emslie研究项目的重点是设计和合成独特的含金属分子（通常是高活性分子），这可以为化学键和反应性提供新的理解，并可以推进特定的应用。这些应用包括催化反应来制造新的有机分子和材料，包括聚合物，在微处理器和存储设备制造中沉积目前难以获得的超薄膜的方法，以及分离锕系金属和其他金属的化学技术。在研究领域1，我们将合成罕见的刚性金属结合分子（配体），这些分子被设计为严格控制特定目的的金属结合环境。这些配体将用于制备和研究极为罕见的稀土、锕系元素和4族烷基标记物的结构，这些标记物既具有高活性又具有热稳定性，从而能够研究它们的结构和反应性，并开发在催化（例如烯烃聚合和氢元化）方面的应用。此外，它们将用于制备具有前所未有的锕系元素配体相互作用的锕系元素配合物。这些分子的研究将有助于更好地理解锕系元素配合物中的键合，并可能为改进环境放射化学中锕系元素的分离和锕系元素的回收方法指明方向。研究领域二是利用原子层沉积（ALD）技术合成和应用高活性分子（含有金属-碳键的分子）用于薄膜沉积。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，这将是未来微处理器和存储设备所需要的，特别是当需要在具有纳米级特征的表面（如深沟槽）上沉积时。然而，ALD中的膜生长依赖于分子之间基于表面的反应，在许多情况下，合适的分子和反应尚未被设想出来。纯金属的热ALD尤其具有挑战性，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，使ALD目前难以获得的早期和中期过渡金属薄膜；那些需要制造未来技术设备的人。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途径，这些分子具有与硅等元素具有多重键的配体。这项工作建立在最近Emslie小组在锰化学方面的几篇论文的基础上，并针对罕见或前所未有的金属-配体相互作用的基本兴趣。结构，键合，以及由此产生的含金属分子的反应性将被研究，以及它们在催化反应中的潜在参与，如烯烃硅氢化，将被探索。

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.