Discovery of New Catalysts for Functionalization of Molecular Nitrogen

氮分子功能化新催化剂的发现

• 批准号: RGPIN-2020-04247
• 负责人: Fryzuk, Michael
• 金额: $ 1.75万
• 依托单位: University of British Columbia
• 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=716857
• 关键词: Discovery; New; Catalysts; Functionalization; Molecular

This is a resubmission of NSERC Discovery grant from 2018, which garnered one-year funding at $24K. In this proposal I have removed some of the high-risk, blue-sky ideas that were met with criticism by one of five external referees. One of the unmet challenges in chemistry is the discovery of an efficient yet mild process for the conversion of molecular nitrogen (N2) into higher value organonitrogen containing species, such as amines or nitrogen-containing heterocycles. The wellknown production of ammonia via the Haber-Bosch process is over 100 years old, and is still the only process that uses N2 as a feedstock on an industrial scale. In contrast, the isoelectronic CO molecule is used in a variety of different industrial processes, such as hydroformylation, the acetic acid synthesis, and carbonylation. The fact that even after more than 100 years there is still no new industrial process that uses molecular nitrogen as a feedstock is a reminder of the difficulty of the problem of using this unreactive small molecule in an industrial setting. This proposal seeks to both discover and optimize catalytic reactions that convert molecular nitrogen into higher value organic materials. We have made seminal contributions to stoichiometric activation of dinitrogen (N2) that have spanned almost three decades. However, recently, we have discovered a unique catalytic system that very efficiently converts N2 into N(SiMe3)3 with turnover numbers that rival the best reports from other researchers worldwide. Building on this exciting result is the focus of the ideas presented in this Discovery Grant application. Not only do we want to optimize this process by examining new ligand designs and new base metal combinations, but we also want to expand this reaction to generate nitrogen-carbon bonds catalytically by adapting the aforementioned catalytic formation of N(SiMe3)3. Success in this project will be in the form of publications in high impact journals and the continued training of highly qualified personnel who will be ready to tackle important chemical problems of societal importance.

这是2018年NSERC发现补助金的重新提交，该补助金获得了2.4万美元的一年资金。在这个建议中，我删除了一些高风险的、不切实际的想法，这些想法遭到了五位外部裁判之一的批评。化学中未解决的挑战之一是发现一种有效而温和的方法，用于将分子氮（N2）转化为更高价值的含有机氮物质，例如胺或含氮杂环。众所周知的通过Haber-Bosch工艺生产氨已有100多年的历史，并且仍然是唯一一种在工业规模上使用N2作为原料的工艺。相比之下，等电子CO分子用于各种不同的工业过程，例如加氢裂化、乙酸合成和羰基化。即使在100多年后，仍然没有使用分子氮作为原料的新工业方法的事实提醒人们在工业环境中使用这种不反应的小分子的困难问题。 该提案旨在发现和优化将分子氮转化为更高价值的有机材料的催化反应。我们已经作出了开创性的贡献，化学计量活化的二氮（N2），已经跨越了近三十年。然而，最近，我们发现了一种独特的催化系统，可以非常有效地将N2转化为N（SiMe 3）3，其转化率可以与全球其他研究人员的最佳报告相媲美。 建立在这个令人兴奋的结果是在这个发现补助金申请提出的想法的重点。我们不仅希望通过研究新的配体设计和新的贱金属组合来优化这一过程，而且还希望通过调整上述N（SiMe 3）3的催化形成来扩展这一反应以催化生成氮-碳键。这一项目的成功将体现在高影响力期刊上的出版物和对高素质人员的持续培训上，这些人员将随时准备解决具有社会重要性的重要化学问题。