RUI: Primary and Secondary Coordination Sphere Effects in Ruthenium-Catalyzed Base-Free Hydrogen Transfer Reactions

RUI：钌催化无碱氢转移反应中的初级和次级配位球效应

• 批准号: 2246470
• 负责人: Steven Kalman
• 金额: $ 21.96万
• 依托单位: Stockton 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: 2023-09-01 至 2026-08-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2246470&HistoricalAwards=false
• 关键词: RUI; Primary; Secondary; Coordination; Sphere

With support from the Chemical Catalysis Program in the Division of Chemistry, Steven Kalman of Stockton University is studying the development of new catalysts that can add hydrogen to organic compounds (hydrogenation). These reactions are important for making products ranging from pharmaceuticals to fragrances and any number of fine chemicals. Traditionally these types of reactions are done using specialized equipment and hydrogen gas. The work proposed here bypasses the storage of hydrogen by generating hydrogen during the reaction from readily available precursors. Another emphasis of this research is to make the reactions simpler and less expensive. This will be done through design by constructing catalysts that perform hydrogenations using mild conditions. This funding will support the work of undergraduate students from diverse backgrounds by providing training in various chemistry techniques and an immersive summer research experience. This unique opportunity is preparing them for both obtaining advanced degrees in science fields and contributing to a globally competitive STEM (science, technology, engineering and mathematics) workforce.The hydrogenation of double and triple bonds is an important reaction in the synthesis of various organic compounds. Transfer hydrogenation is a reaction that uses an easily handled reagent like isopropyl alcohol as a substitute for hydrogen gas, negating the use of specialized equipment associated with using gaseous reagents. Most catalysts for this reaction require the use of base additives and/or an atmosphere free of oxygen and moisture. Dr. Kalman and his research group are developing new ruthenium catalysts based on imidazole carboxamide ligands that operate under aerobic conditions and without additives, which allows for a simpler and less expensive reaction setup. These catalysts operate by metal-ligand cooperation in which the ligand participates in the bond breaking and bond forming steps rather than acting solely as a spectator in the reaction. Specifically, Dr. Kalman and his students are studying how modifications to the ligand structure impact the catalytic activities of the ruthenium complexes, leading to the development of more active and selective catalysts. Further, they are applying these new catalysts to other organic reactions such as acceptorless dehydrogenation, a reaction that is important in both organic synthesis and hydrogen storage.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.

在化学催化计划的支持下，斯托克顿大学的史蒂文·卡尔曼（Steven Kalman）正在研究新催化剂的开发，这些催化剂可以为有机化合物（氢化）添加氢。这些反应对于制造从药品到香料和任何数量的精细化学物质的产品非常重要。传统上，这些类型的反应是使用专用设备和氢气进行的。此处提出的工作绕过了氢的储存，该氢在反应期间从随时可用的前体产生氢。这项研究的另一个重点是使反应更简单，更便宜。这将通过设计通过构建使用轻度条件进行氢化的催化剂来完成。这项资金将通过提供各种化学技术和沉浸式夏季研究经验的培训来支持来自不同背景的本科生的工作。这个独特的机会是为他们准备在科学领域获得高级学位，并为全球竞争性茎（科学，技术，工程和数学）劳动力做出贡献。双键和三键的氢化是各种有机化合物的合成的重要反应。转移氢化是一种反应，使用易于处理的试剂（例如异丙醇）作为氢气的替代品，否定了与使用气态试剂相关的专用设备的使用。大多数用于此反应的催化剂都需要使用碱添加剂和/或没有氧气和水分的气氛。 Kalman博士和他的研究小组正在基于在有氧条件下且没有添加剂的情况下运行的咪唑羧酰胺配体开发新的芳族催化剂，这允许进行更简单，更便宜的反应设置。这些催化剂通过金属配体合作运行，其中配体参与键断裂和键形成步骤，而不是仅充当反应中的观众。具体而言，Kalman博士和他的学生正在研究配体结构的修饰如何影响芳族综合体的催化活性，从而导致更活跃和选择性的催化剂的发展。此外，他们将这些新催化剂应用于其他有机反应，例如无受体脱氢作用，这种反应在有机合成和氢存储中都很重要。该奖项反映了NSF的法定任务，并被认为是通过基金会的知识分子优点通过评估来支持的。和更广泛的影响审查标准。