New Paradigms in Main Group Element Assembly and Catalysis

主族元素组装与催化新范式

• 批准号: RGPIN-2019-04529
• 负责人: Rivard, Eric
• 金额: $ 6.85万
• 依托单位: University of Alberta
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2020
• 资助国家: 加拿大
• 起止时间: 2020-01-01 至 2021-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=714711
• 关键词: New; Paradigms; Main; Group; Element

Overview. Main group elements are Earth abundant and form essential components of modern electronics, LEDs, and household products. In this proposal we build upon our research team's prior experience in fundamental inorganic chemistry to address the following pressing questions: a) Can we deposit conducting or insulating components for advanced optoelectronic applications without the need for highly toxic chemicals or harsh conditions? b) Can we coax inexpensive main group elements into performing catalytic transformations previously reserved for expensive metals? We use carbon-based ligands to intercept reactive hydrogen-rich main group species, termed hydrides. These hydrides are often found as free entities in exotic locals such as in interstellar space or at high temperatures. Our work seeks to harness the reactivity of hydrides to accomplish metal-free catalysis or advanced material synthesis under mild conditions. NMR, IR and UV-vis spectroscopy are used to monitor reaction progress and X-ray crystallography to identify new molecular structures. Gel permeation chromatography and thermal analyses (TGA/DSC) allow us to characterize polymers, while computational methods serve as vital predictive tools to evaluate potential reaction paths. We collaborate with experts worldwide and such interactions will help us design/test new batteries and olefin polymerization catalysts. Our proposed program is grouped along three interconnected themes: 1. Mild Deposition of Conductors and Insulators. Traditionally electroactive components have been incorporated into devices using high-temperatures and toxic gaseous precursors. However the harsh nature of these methods places a limit on the types of materials that can be deposited. We will take advantage of the rapid, solution-based, formation of various element hydrides (such as germanium(II) dihydride) and their mild conversion into pure element films, nanomaterials and polymers for use in next generation solar cells and batteries. We will also develop precursors to the highly sought insulator boron nitride, currently prepared at >1500 C. 2. Non-innocent Lewis Acidic Ligands for Catalysis. We will explore a new class of ligand that combines a high degree of steric coverage with the advantageous reactivity inherent to electron deficient (Lewis acidic) groups. The close proximity of these electron deficient ligands to reactive main group centers should encourage cooperative interactions, leading to improved catalytic activity. 3. Anionic N-Heterocyclic Olefins. We recently prepared a series of carbon-based ligands termed anionic N-heterocyclic olefins (aNHOs). We will harness the donor ability of aNHOs to access a series of low-coordinate main group compounds that are pre-designed to act as olefin polymerization catalysts (a billion dollar industry). These aNHO ligands will also be used to tackle a long-standing challenge in industry: the mild catalytic formation of ammonia from abundant nitrogen gas.

概述。主要的群体元素是地球丰富的，形成了现代电子，LED和家用产品的重要组成部分。在此提案中，我们基于研究团队先前在基本无机化学方面的经验来解决以下紧迫问题：a）我们是否可以为高级光电应用程序存放导电或绝缘的组件，而无需严重有毒的化学物质或恶劣的条件？ b）我们可以哄骗便宜的主要组元素来执行先前保留用于昂贵金属的催化转化吗？ 我们使用碳基配体来拦截称为Hydrides的富含反应性氢的主要种类。这些氢化物通常在异国当地人（例如星际空间或高温下）中被发现为自由实体。我们的工作旨在利用氢化物的反应性，以在轻度条件下完成无金属催化或晚期材料合成。 NMR，IR和UV-VIS光谱法用于监测反应进度和X射线晶体学以鉴定新的分子结构。凝胶渗透色谱和热分析（TGA/DSC）使我们能够表征聚合物，而计算方法则是评估潜在反应路径的重要预测工具。我们与全球专家合作，此类互动将有助于我们设计/测试新电池和烯烃聚合催化剂。 我们提出的计划按三个相互联系的主题分组： 1。导体和绝缘子的轻度沉积。传统上，电活性成分已使用高温和有毒的气态前体纳入设备中。但是，这些方法的苛刻性质限制了可以存放的材料类型。我们将利用各种元素氢化物（例如葡萄球菌（II）二氢乙酯）的快速，基于溶液的形成以及将其温和转化为纯元素膜，纳米材料和聚合物，用于下一代太阳能电池和电池。我们还将为目前在> 1500 C中准备的备受追捧的绝缘体氮化物开发前体。 2。非自然的刘易斯酸性配体进行催化。我们将探索一类新的配体，该配体将高度的空间覆盖范围与缺乏电子（刘易斯酸性）基团固有的有利反应性结合在一起。这些电子缺乏配体与反应性主组中心的密切接近应鼓励合作相互作用，从而改善催化活性。 3。阴离子N-杂环烯烃。我们最近准备了一系列称为阴离子N-杂环烯烃（ANHOS）的碳基配体。我们将利用Anhos的供体能力访问一系列低坐标的主要组化合物，这些化合物是预先设计的，可以充当烯烃聚合催化剂（十亿美元的行业）。这些Anho配体还将用于应对行业中的长期挑战：大量的氮气中氨的催化形成。