Cation-Controlled Catalysis with Pincer-Crown Ether Complexes

在化学系化学催化计划的支持下，北卡罗来纳大学教堂山分校的亚历山大·米勒将研究简单离子控制催化有机转化结果的能力。将制备定义明确的催化剂，并测试其在添加离子时改变其结构和功能的能力。此外，该项目将为培训不同群体的学生提供一个平台，学习化学合成、热力学和动力学机理分析以及催化剂开发。这种阳离子控制的催化很可能提供获得特定的烯烃异构体的途径，这些异构体在香料、制药和日用化学工业中很有价值，但目前很难获得。该项目将通过一个网络资源，即“安全网”，对更广泛的化学界产生影响，该网络汇集了化学研究实验室的标准操作程序，以便广泛传播，以改进安全文化。在这项研究中，Alexander Miller博士和他在北卡罗来纳大学教堂山分校的研究团队将研究如何利用阳离子-大环相互作用来控制涉及烯烃的催化转化的选择性。含有大环的“钳形-冠醚”配体将为理解非共价相互作用如何影响催化剂的结构和反应活性提供多种平台。一个特别的重点将是制定基于底物-催化剂或离子-催化剂相互作用来控制催化剂选择性的策略。这些研究的方法是将催化研究与详细的热力学和动力学机制测试相结合，以阐明离子控制催化的设计原则。这些适应性强的“响应性催化剂”将允许探索非共价控制催化的新概念。这项研究将为改进催化剂的设计和开发提供基础知识。该奖项反映了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 the support of the Chemical Catalysis Program in the Division of Chemistry, Alexander Miller of the University of North Carolina-Chapel Hill will study the ability of simple ions to control the outcomes of catalytic organic transformations. Well-defined catalysts will be prepared and tested for their ability to alter their structure and function upon addition of ions. In addition, the project will provide a platform for training a diverse group of students in chemical synthesis, thermodynamic and kinetic mechanistic analysis, and catalyst development. Such cation-controlled catalysis will likely provide access to specific alkene isomers that are valuable in the fragrance, pharmaceutical, and commodity chemical industries, but are currently difficult to obtain. The project will impact the broader chemistry community through a web-based resource, namely the “Safety Net”, that assembles standard operating procedures from chemistry research laboratories for broad dissemination to improve the culture of safety. In this research, Dr. Alexander Miller and his research team at the University of North Carolina-Chapel Hill will study how cation–macrocycle interactions can be harnessed to control the selectivity of catalytic transformations involving alkenes. Macrocycle-containing “pincer-crown ether” ligands will provide versatile platforms, when appended to catalytically active metal centers, for understanding how non-covalent interactions influence catalyst structure and reactivity. A particular focus will be on the development of strategies to control catalyst selectivity based on either substrate–catalyst or ion–catalyst interactions. The approach to these studies is to pair catalysis studies with detailed thermodynamic and kinetic mechanistic examinations to elucidate the design principles of ion-controlled catalysis. These adaptable “responsive catalysts” will allow for the exploration of new concepts in non-covalently controlled catalysis. The research will provide foundational knowledge for improved catalyst design and development.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.