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.

在化学系化学催化项目的支持下，斯托克顿大学的史蒂文·卡尔曼正在研究一种新型催化剂的开发，这种催化剂可以将氢添加到有机化合物中（氢化）。这些反应对于制造从药品到香水和任何精细化学品的产品都很重要。传统上，这些类型的反应是使用专门的设备和氢气来完成的。这里提出的工作绕过了氢的储存，在反应过程中从现成的前体产生氢。这项研究的另一个重点是使反应更简单，成本更低。这将通过设计构建在温和条件下进行氢化的催化剂来实现。这笔资金将通过提供各种化学技术的培训和身临其境的夏季研究经验，支持来自不同背景的本科生的工作。这个独特的机会使他们为获得科学领域的高级学位做好准备，并为具有全球竞争力的STEM（科学、技术、工程和数学）劳动力做出贡献。双键和三键的氢化反应是合成各种有机化合物的重要反应。转移加氢是一种使用易于处理的试剂，如异丙醇作为氢气的替代品的反应，不需要使用与使用气体试剂相关的专门设备。这种反应的大多数催化剂需要使用碱性添加剂和/或无氧和无水分的气氛。卡尔曼博士和他的研究小组正在开发一种基于咪唑羧酰胺配体的新型钌催化剂，这种催化剂在有氧条件下运行，不含添加剂，这使得反应装置更简单，成本更低。这些催化剂通过金属与配体的配合作用起作用，其中配体参与断键和成键步骤，而不是仅仅作为反应的旁观者。具体来说，卡尔曼博士和他的学生正在研究配体结构的修饰如何影响钌配合物的催化活性，从而开发出更具活性和选择性的催化剂。此外，他们正在将这些新催化剂应用于其他有机反应，如无受体脱氢，这一反应在有机合成和储氢中都很重要。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。