Abundant transition metals in catalysis

催化作用中丰富的过渡金属

• 批准号: RGPIN-2018-04899
• 负责人: Morris, Robert
• 金额: $ 15.3万
• 依托单位: University of Toronto
• 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=748357
• 关键词: Abundant; transition; metals; catalysis

Our program will focus on the discovery of new catalysts based on the sustainable metals manganese, cobalt and iron. Industry is striving to replace catalysts based on platinum group metals that are precious and rare with these more abundant metals that are cheaper, more benign to human health and more appropriate for green chemical processes. Our catalysts will allow effective and new syntheses of amines of importance in making pharmaceuticals, agrochemicals and polymers, and alcohols with applications in pharma, fragrances and green energy storage. In the past five years we developed state-of-the-art catalysts (the FeATHerII and FeATHerIII catalysts) for asymmetric transfer hydrogenation (ATH) of ketones and certain imines, and more recently for the asymmetric pressure hydrogenation of ketones using iron and manganese. With this success, my research team has grown to eleven graduate students, 8 domestic and 3 co-supervised (U. Muenster), along with visitors and undergraduates a powerful catalyst discovery team. We will use our proven experimental and computational approaches to discover new catalysts that are easier and safer to synthesize, more active, productive and selective and more robust with respect to oxygen and deactivation routes. Like enzymes, our catalysts will be designed with complementary groups on the ligand to those of imines and ketones to dramatically improve catalytic enantioselectivity in the production of alcohols and amines of value to the pharmaceutical and fine chemical industries. We will use our skill in ligand synthesis and computational modelling to build in hydrogen bond donors and acceptors using established methods. Our phosphine aldehyde precursors are an ideal starting point for this chemistry. These new metal complexes will be applied to a variety of important asymmetric reactions in organic synthesis including hydrosilylation, hydroboration and carbon-carbon bond forming. A more recent feature is the use of N-heterocyclic carbene donors tethered with primary or secondary amines (e.g. enantiopure Kaibene discovered by graduate student Kai Wan) that provide a real boost in activity. Our ligand acidity constant (LAC) equation that was first described in 2014 for predicting the acidity of hydride and dihydrogen complexes has significant implications for catalyst design. It will be used to explore and guide the synthesis of catalysts that are tolerant to the acidic conditions of carbon dioxide reduction to liquid fuels and imine hydrogenation. We will measure the acidity of paramagnetic metal hydride complexes and use state of the art computational tools to understand the factors that determine their acidity. To assist in the hot field of catalytic carbon-hydrogen bond functionalization we will extend the LAC concepts both experimentally and computationally to coordinated (agostic) carbon-hydrogen bonds.

我们的计划将专注于发现基于可持续金属锰，钴和铁的新催化剂。 工业界正在努力用更便宜、对人类健康更有利和更适合于绿色化学过程的这些更丰富的金属来取代基于铂族金属的催化剂，铂族金属是珍贵和稀有的。 我们的催化剂将允许有效的和新的合成胺的重要性，在制造药物，农用化学品和聚合物，和醇与应用在制药，香料和绿色能源储存。 在过去的五年中，我们开发了最先进的催化剂（FeATHerII和FeATHerIII催化剂），用于酮和某些亚胺的不对称转移氢化（ATH），最近又开发了使用铁和锰的酮的不对称加压氢化。 有了这个成功，我的研究团队已经发展到11个研究生，8个国内和3个共同监督（美国）。明斯特），沿着的游客和大学生一个强大的催化剂发现团队。 我们将使用我们成熟的实验和计算方法来发现新的催化剂，这些催化剂更容易合成，更安全，更活跃，更有生产力和选择性，并且在氧气和失活途径方面更强大。 与酶一样，我们的催化剂将在配体上设计有与亚胺和酮的配体互补的基团，以显着提高对医药和精细化工行业有价值的醇和胺的生产中的催化对映选择性。我们将利用我们在配体合成和计算建模方面的技能，使用已建立的方法建立氢键供体和受体。我们的膦醛前体是这种化学的理想起点。这些新的金属配合物将被应用于有机合成中的各种重要的不对称反应，包括硅氢加成、硼氢化和碳-碳键的形成。 最近的特征是使用与伯胺或仲胺（例如，由研究生Kai Wan发现的对映体纯Kaibene）连接的N-杂环卡宾供体，其提供活性的真实的提高。 我们的配体酸度常数（LAC）方程于2014年首次描述，用于预测氢化物和二氢络合物的酸度，对催化剂设计具有重要意义。它将被用于探索和指导耐二氧化碳还原为液体燃料和亚胺氢化的酸性条件的催化剂的合成。我们将测量顺磁性金属氢化物络合物的酸度，并使用最先进的计算工具来了解决定其酸度的因素。 为了帮助催化碳-氢键功能化的热点领域，我们将实验和计算两方面的LAC概念扩展到协调（agostic）碳-氢键。