Exploring new experimental space with inversely-polarized phosphaalkenes and dianionic pincer ligands

用反极化磷烯和双阴离子钳配体探索新的实验空间

• 批准号: RGPIN-2017-05665
• 负责人: Lavoie, Gino
• 金额: $ 1.6万
• 依托单位: York 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=747965
• 关键词: Exploring; new; experimental; space; inversely

Double bonds play a crucial role in synthetic chemistry. Simple olefins, such as ethylene, propylene, acrylates and other related functionalized olefins are important building blocks for the polymer industry. The reactivity of C=C double bonds can also undergo alkene metathesis (and alkyne metathesis for CC triple bonds) to create new value-added chemicals and materials used across the industry, from fine chemicals to perfumes, pharmaceuticals and polymers. Similarly, polar double bonds such as C=O and C=N are hydrogenated into high-value molecules, with the possibility to introduce a new chiral centre in the molecule with biological activity. Developing a solid fundamental understanding of catalysis is essential for the industry to have access to better (more stable, more active and more selective) catalysts that can mediate important transformations with a wide range of substrates. The proposed research program will allow us to explore and demonstrate the scope and utility of two classes of ancillary ligands that have remained largely unexplored in homogeneous catalysis: inversely-polarized phosphaalkenes and dianionic pincer (XLY2) ligands. These will be investigated in the context of olefin metathesis, polymerization, double bond hydrogenation and water oxidation. Both classes of ligands offer tremendous opportunities to impact the field of catalysis in general, as tertiary phosphines, N-heterocyclic carbenes and monoanionic pincer ligands have in the past decades. They ligands open up new unexplored experimental space, while providing remarkable control over the sterics and electronics about the metal. In the course of the program, the coordination chemistry of cobalt will be extensively studied to expand the use of this earth-abundant metal in catalytic transformations often dominated by more expensive and rare precious metals. The study of these well-defined transition metal complexes will provide valuable fundamental knowledge and great insight into critically-important catalytic transformations, including water oxidation.

双键在合成化学中起着至关重要的作用。单烯烃，如乙烯、丙烯、丙烯酸酯和其他相关的官能化烯烃，是聚合物工业的重要组成部分。C=C双键的反应性还可以进行烯烃歧化反应(以及CC三键的烯烃歧化反应)，以创造新的增值化学品和材料，用于整个行业，从精细化学品到香水、药品和聚合物。类似地，C=O和C=N等极性双键被氢化成高价值分子，有可能在具有生物活性的分子中引入新的手性中心。发展对催化的扎实的基础知识对于该行业获得更好的(更稳定、更活性和更有选择性的)催化剂至关重要，这些催化剂可以通过广泛的底物来调解重要的转化。拟议的研究计划将使我们能够探索和展示两类在均相催化中仍然很大程度上未被探索的辅助配体的范围和用途：反极化的磷杂烯和双阴离子钳形(XLY2)配体。这些将在烯烃歧化、聚合、双键加氢和水氧化的背景下进行研究。这两类配体都提供了影响催化领域的巨大机会，就像叔膦、N-杂环卡宾和单阴离子钳形配体在过去几十年中所做的那样。它们的配体开辟了新的未被探索的实验空间，同时提供了对金属的立体和电子学的非凡控制。在该计划过程中，将广泛研究钴的配位化学，以扩大这种富含稀土的金属在催化转化中的用途，这些转化通常由更昂贵和稀有的贵金属主导。对这些定义明确的过渡金属络合物的研究将为包括水氧化在内的至关重要的催化转化提供宝贵的基础知识和深刻的见解。