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

用于催化、锕系络合和薄膜沉积的反应性有机金属配合物和配体设计

• 批准号: RGPIN-2020-06794
• 负责人: Emslie, David
• 金额: $ 4.66万
• 依托单位: McMaster University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2021
• 资助国家: 加拿大
• 起止时间: 2021-01-01 至 2022-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=741438
• 关键词: Reactive; Organometallic; Complexes; Ligand; Design

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.

EMSLIE研究计划的重点是设计和合成独特的含金属分子（通常是高反应性分子），这些分子可以提供对化学键和反应性的新理解，并可以推进特定的应用。这些应用包括制造新的有机分子和材料（包括聚合物）的催化反应，在微处理器和记忆装置制造过程中沉积目前无法接近的超薄膜的方法，以及化学技术，以将actinide金属与其他金属分开。 在研究区域1中，我们将合成不常见的刚性金属结合分子（配体），这些分子（配体）旨在为特定目的严格控制金属结合环境。这些配体将用于制备和研究极为罕见的稀土，actacinide和4组烷基分解的结构，它们既具有高反应性和热稳定性，从而实现了其结构和反应性的研究，以及催化中应用的发展（例如，烯烃聚合和水力元素）。此外，它们将用于制备具有前所未有的acti肌相互作用的阳离子化合物。对这些分子的研究将更好地理解actacinide复合物中的键合，并可能指向改善环境放射化学和actinide回收中静脉分离方法的道路。 研究区域2专注于使用原子层沉积（ALD）的高反应性分子（包含金属碳连接的分子（包含金属碳连接的分子））的合成和应用。可以说，ALD是唯一能够沉积超薄且高度保形（即表面拥抱）膜的技术，在将来的微处理器和记忆设备中需要，尤其是在具有纳米尺度特征（例如深处沟槽）表面上需要沉积的时候。然而，ALD的膜生长依赖于分子之间的基于表面的反应，在许多情况下，尚未想到合适的分子和反应。纯金属的热量特别具有挑战性，并且在大多数早期和中期金属中尚未实现。在这项研究中，我们将开发独特的分子和反应，以实现当前无法访问的早期和中过渡金属薄膜的ALD；制造未来技术设备所需的人。在研究区域3中，我们将致力于开发含金属分子的广泛新途径，这些新路线具有与硅等元素多种键的配体。这项工作建立在锰化学中最近的一些Emslie集团出版物上，并以基本兴趣的罕见或前所未有的金属配体相互作用为目标。将研究所产生的金属分子的结构，键和反应性，并将探索它们在催化反应（例如烯烃氢硅烷基）中的潜在参与。