Hyperpolarization Catalysts for in situ Mechanistic Studies

用于原位机理研究的超极化催化剂

• 批准号: 2324961
• 负责人: Alison Fout
• 金额: $ 47.5万
• 依托单位: Texas A&M University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-04-01 至 2024-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2324961&HistoricalAwards=false
• 关键词: Hyperpolarization; Catalysts; situ; Mechanistic; Studies

With funding from the Chemical Synthesis Program in the Chemistry Division, Alison Fout in the Department of Chemistry at the University of Illinois Urbana-Champaign, will develop new cobalt-based compounds that can facilitate the reactions of hydrogen in important chemical processes. Hydrogen is an extremely important chemical feedstock that is used a wide variety of chemical processes. However, by itself it does not react or reacts very slowly. To circumvent this problem a number of metal compounds have been developed that activate hydrogen and greatly speed its rate of reactions. These compounds are called catalysts and almost all are based on expensive, rare metals. This project studies the ability of a less expensive metal, cobalt, to activate hydrogen. As the details of how hydrogen adds to various compounds is difficult to determine, an unusual form of hydrogen known as parahydrogen will be used in this study to increase the sensitivity of measurements up to 200,000 times. In addition, the project aims to improve diversity, equity, and inclusion in the next generation of scientists. Prof. Fout and her students will participate in the 3M Summer Scholars Program, which aims to provide research experiences to undergraduate students from underrepresented groups, the Next Generation Illinois Scientist, which engages elementary students in rural schools, and the Bonding Camp for Girls, which targets 6-8th grade girls.This project synthesizes cobalt complexes that may serve as parahydrogen-induced polarization (PHIP) catalysts. This requires diamagnetic complexes that remain S=0 throughout the catalytic cycle for both direct and indirect hyperpolarization. To achieve this and to access a Co(I)/Co(III) catalytic cycle, complexes of ligands containing electron-rich moieties and carbenes are prepared. Their activity to catalyze PHIP is evaluated across a range of substrates including olefins, alkynes, and arenes, which feature long-relaxing nuclei in their functional groups. Some of the substrates are key reactants in polymerization catalysis. In these cases, the PHIP effect is used to detect and study of mechanistic intermediates that have not previously been observed.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

随着化学综合计划在化学部门的资金，伊利诺伊州乌尔巴纳 - 奇普尼亚大学化学系的艾莉森·福特（Alison Fout）将开发出新的基于钴的化合物，以促进氢在重要化学过程中的反应。氢是一种非常重要的化学原料，用于多种化学过程。但是，它本身不会反应或反应非常缓慢。为了解决这个问题，已经开发了许多金属化合物，可激活氢并大大加速其反应速度。这些化合物称为催化剂，几乎所有化合物都基于昂贵的稀有金属。该项目研究了较便宜的金属钴激活氢的能力。由于难以确定氢如何添加氢的细节，因此将在本研究中使用一种不寻常的氢形式，称为寄生虫，以提高测量的敏感性高达200,000次。此外，该项目旨在改善下一代科学家的多样性，公平性和包容性。 Fout教授和她的学生将参加3M夏季学者计划，该计划旨在为来自代表性不足的群体的本科生提供研究经验，下一代伊利诺伊州科学家，该学生在农村学校中吸引小学的学生以及女孩的纽带营地，该群体对6至8年级的女生进行了目标。这需要在直接和间接超极化的整个催化循环中保持S = 0的磁磁复合物。为了实现这一目标并访问CO（i）/CO（iii）催化循环，制备了含有富含电子的部分的配体的配合物。它们在包括烯烃，炔烃和竞技场在内的一系列底物中评估了它们的催化PHIP的活性，这些底物具有官能团的长片核。一些底物是聚合催化中的关键反应物。在这些情况下，PHIP效应用于检测和研究以前尚未观察到的机械中间体。该奖项反映了NSF的法定任务，并被认为是值得通过基金会的智力优点和更广泛的影响评估的评估来进行评估的。