Unlocking Photoswitchable Main-group Catalysis Using Azophosphines

使用偶氮膦解锁光切换主族催化

• 批准号: EP/W036908/1
• 负责人: Andrew Jupp
• 金额: $ 45.43万
• 依托单位: University of Birmingham
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2023
• 资助国家: 英国
• 起止时间: 2023 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FW036908%2F1
• 关键词: Unlocking; Photoswitchable; Main; group; Catalysis

Catalysts are substances that make chemical reactions more efficient and are crucial to the chemical industry; in fact, 90% of commercial chemicals involve at least one catalytic step in their production. A high proportion of these catalysts rely on precious metals (e.g., palladium, platinum, gold and rhodium); it is forecast that the global precious metal catalysts market will reach $26.73 billion by 2026. And yet precious metals have several disadvantages, predominantly arising from the fact that they are precious, i.e., they are scarce and very expensive. There is a huge economic cost associated with mining these low-abundance metals, and an increasing environmental cost with extracting and processing the ore that is leading to an increase in fossil fuel usage and carbon dioxide emissions. With a pressing need to better manage the planet's resources, we urgently need to find more sustainable alternatives to support the chemical industry of the future.The proposed research will drive forward the use of catalysts made from cheap and abundant elements, such as nitrogen, phosphorus, and boron, in systems known as Frustrated Lewis Pairs (FLPs). Most of the previous FLP catalysts that have been explored are air-sensitive, and require specialist techniques when using them, which has limited their uptake by organic chemists and more widely in industry. The research in this proposal will focus on the design of a new family of molecules that can change shape when light is shone on them, and can therefore act as switches with "on" or "off" states for catalysis. These new molecules, containing phosphorus and nitrogen as the key elements, will be used within an FLP that is stable and inactive under normal conditions ("off" state), but can be activated with light to become a functional metal-free catalyst ("on" state). The bench-stable precursors (pre-catalysts) will make FLP catalysis accessible to a broader academic and industrial audience.The project represents a priority area for the UK, and aligns strongly with the EPSRC's themes of Physical Sciences and Manufacturing the Future. It also tallies with the United Nations (UN) Sustainable Development Goals, specifically Goal 9: 'Industry, Innovation and Infrastructure.'

催化剂是使化学反应更有效且对化学工业至关重要的物质。实际上，90％的商业化学物质至少涉及其生产中的催化步骤。这些催化剂中很大一部分依赖于贵金属（例如钯，铂，金和若ix）；据预测，到2026年，全球贵金属催化剂市场将达到267.3亿美元。然而，贵金属却有几种缺点，主要是由于它们是珍贵的，即它们稀缺且非常昂贵。挖掘这些低含量金属的经济成本巨大，并且通过提取和加工矿石的矿石的矿石成本增加，这导致化石燃料的使用和二氧化碳排放的增加。迫切需要更好地管理地球的资源，我们迫切需要找到更多可持续的替代方案来支持未来的化学工业。拟议的研究将推动使用由廉价和丰富元素制成的催化剂，例如氮，磷和硼，例如在被称为“沮丧的Lewis Pairs Pairs”的系统中。以前探索的大多数FLP催化剂都对空气敏感，并且在使用时需要专业技术，这限制了有机化学家的吸收，并且在行业中更广泛。该提案中的研究将集中于新的分子家族的设计，这些分子可以在其上发光时会改变形状，因此可以用作“ ON”或“ OFF”状态进行催化的开关。这些新的分子将含磷和氮作为关键要素，将在正常条件下稳定且不活跃的FLP中使用（“ OFF”状态），但可以用光激活以成为无官能金属的催化剂（“ ON”状态）。基准稳定的前体（前催化剂）将使更广泛的学术和工业受众可以使用FLP催化。该项目代表了英国的优先领域，并且与EPSRC的体育科学主题和制造未来都非常相吻合。它还与联合国（联合国）可持续发展目标有关，特别是目标9：“行业，创新和基础设施”。

项目成果

Azophosphines: Synthesis, Structure and Coordination Chemistry

偶氮膦：合成、结构和配位化学

• DOI: 10.26434/chemrxiv-2024-4kmw8
• 发表时间: 2024
• 作者: Jordan E

Synthesis and Reactivity of the [NCCCO]- Cyanoketenate Anion

[NCCCO]-氰基烯酸根阴离子的合成和反应性

• DOI: 10.26434/chemrxiv-2024-qv8jh
• 发表时间: 2024
• 作者: Wang T