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

在化学系化学催化项目的支持下，斯托克顿大学的史蒂文·卡尔曼正在研究可以为有机化合物加氢(氢化)的新型催化剂的开发。这些反应对制造从药品到香水和任何数量的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进行的。这里提出的工作绕过了氢的储存，在反应过程中从容易获得的前体中产生氢。这项研究的另一个重点是使反应更简单，成本更低。这将通过设计建造使用温和条件进行加氢的催化剂来实现。这笔资金将通过提供各种化学技术培训和身临其境的暑期研究体验，支持来自不同背景的本科生的工作。这一独特的机会为他们在科学领域获得高级学位做好了准备，并为建立一支具有全球竞争力的STEM(科学、技术、工程和数学)劳动力做出了贡献。双键和三键的氢化是各种有机化合物合成中的重要反应。转移加氢是一种使用异丙醇等易于操作的试剂代替氢气的反应，不需要使用与使用气态试剂相关的专门设备。该反应的大多数催化剂需要使用碱性添加剂和/或无氧无湿的气氛。卡尔曼博士和他的研究小组正在开发基于咪唑甲酰胺配体的新型Ru催化剂，这种催化剂可以在有氧条件下运行，不需要添加剂，从而实现了更简单、更便宜的反应装置。这些催化剂通过金属-配体的合作进行操作，其中配体参与了键的断裂和键的形成步骤，而不是仅仅作为反应的旁观者。具体地说，卡尔曼博士和他的学生正在研究配体结构的修改如何影响Ru络合物的催化活性，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氢气存储中都很重要。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

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.