Organometallic Chemistry of the Nonmetals: Unlocking New Approaches to Green Catalysis

非金属有机金属化学：开辟绿色催化新方法

• 批准号: RGPIN-2021-03814
• 负责人: Légaré, MarcAndré
• 金额: $ 2.11万
• 依托单位: McGill University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2022
• 资助国家: 加拿大
• 起止时间: 2022-01-01 至 2023-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=747968
• 关键词: Organometallic; Chemistry; Nonmetals; Unlocking; New

Our research and training program will study new chemistry of the main group elements to turn them into potent and sustainable catalysts for bulk and fine chemical synthesis. One of the great challenges of chemistry in the 21st century is the development of sustainable approaches to the production of chemicals. Catalysis, a concept reckoned as one of the pillars of green chemistry, is currently used by most sectors of the chemical industry in order to provide society with the variety of value-added products it requires. Unfortunately, despite the advantages of catalysis in term of sustainability, the fact that modern catalysts typically rely on transition metals (TMs) in their active site comes with important disadvantage. Indeed, precious transitions metals - elements that are costly, rare in Canada and difficult to extract from natural resources - have the best-developed catalytic chemistry of all the elements of the periodic table. The high price, toxicity and environmentally challenging extraction of TMs is an important limitation in the sustainability and applicability of catalysis. Because they lack the intrinsic reactivity of TMs, the main group elements (MGEs) have long been neglected in catalytic research. MGEs typically lack the redox flexibility and advantageous combination of vacant and filled orbitals that make the TMs ideally suited for catalysis. Our program will find strategies to at the same time address these perceived deficiencies of MGEs and to use their unique characteristics to develop ground-breaking sustainable catalysts for a wide range of applications. Our program has a two-pronged vision: we will not only tackle application-motivated problems by developing metal-free catalysts for industrially-important reactions, but also take a leading role in the fundamental scientific investigation of the chemistry of MGEs and challenge some traditional assumptions regarding their reactivity. Our long term vision is to make MGE part of the mainstream of catalysis. To reach our goals, we will use a rational design approach and build an expertise in predictive computational modelling for all members of the group. With this training, the team will tackle three initial objectives: - To explore the redox-based reactivity of elusive oxidation state of MGEs by developing stable-yet-reactive mono-coordinated complexes. - To develop a new class of carbenes that display complementary s-acidic and p-basic properties to mimic the orbital arrangement of TMs . - To develop MGE catalysts for olefin metathesis compatible with fluorinated olefins. This mixture of ground-breaking advancement of knowledge, of promising green applications, and of state-of-the-art training of HQP will be of great benefit to the Canadian leadership in science and society. Specifically, the industrial interest for green technologies and catalysis that come at a low cost will make scientists trained in the design of MGE-based catalysts a sought-after type of HQP.

我们的研究和培训计划将研究主族元素的新化学，将它们转化为用于批量和精细化学合成的有效且可持续的催化剂。 21 世纪化学面临的巨大挑战之一是开发可持续的化学品生产方法。催化这一概念被认为是绿色化学的支柱之一，目前被化学工业的大多数部门所使用，以便为社会提供所需的各种增值产品。不幸的是，尽管催化在可持续性方面具有优势，但现代催化剂通常在其活性位点依赖过渡金属（TM），这一事实带来了重要的缺点。事实上，贵重的过渡金属——在加拿大昂贵、稀有且难以从自然资源中提取的元素——具有元素周期表中所有元素中最发达的催化化学特性。 TM 的高价格、毒性和对环境的挑战是催化的可持续性和适用性的重要限制。由于缺乏TM的固有反应性，主族元素（MGE）长期以来在催化研究中被忽视。 MGE 通常缺乏氧化还原灵活性以及空轨道和填充轨道的有利组合，而这使得 TM 非常适合催化。我们的计划将找到策略，同时解决 MGE 的这些明显缺陷，并利用其独特的特性为广泛的应用开发突破性的可持续催化剂。我们的计划有一个双管齐下的愿景：我们不仅将通过开发用于工业重要反应的无金属催化剂来解决应用引发的问题，而且还将在 MGE 化学的基础科学研究中发挥主导作用，并挑战一些传统的方法。关于它们的反应性的假设。我们的长期愿景是使 MGE 成为催化主流的一部分。为了实现我们的目标，我们将使用合理的设计方法，并为团队的所有成员建立预测计算建模的专业知识。通过这次培训，该团队将实现三个初步目标： - 通过开发稳定但具有反应性的单配位络合物，探索 MGE 难以捉摸的氧化态的基于氧化还原的反应性。 - 开发一类新型卡宾，其具有互补的 s-酸性和 p-碱性特性，以模仿 TM 的轨道排列。 - 开发与氟化烯烃相容的用于烯烃复分解的MGE催化剂。 这种突破性的知识进步、有前途的绿色应用以及最先进的 HQP 培训的结合将为加拿大在科学和社会方面的领导地位带来巨大好处。具体来说，工业界对低成本绿色技术和催化的兴趣将使接受 MGE 催化剂设计培训的科学家成为受欢迎的 HQP 类型。