Cation-Controlled Catalysis with Pincer-Crown Ether Complexes

在化学系化学催化项目的支持下，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，并测试其在加入离子后改变其结构和功能的能力。 此外，该项目将提供一个平台，培训一组不同的学生在化学合成，热力学和动力学机理分析，催化剂的发展。这种阳离子控制的催化将可能提供获得在香料、制药和日用化学工业中有价值但目前难以获得的特定烯烃异构体的途径。 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，该资源汇集了化学研究实验室的标准作业程序，供广泛传播，以改善安全文化。在这项研究中，北卡罗来纳大学教堂山分校的亚历山大米勒博士和他的研究小组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。含大环的“钳冠醚”配体将提供多功能平台，当附加到催化活性金属中心时，用于理解非共价相互作用如何影响催化剂结构和反应性。一个特别的重点将是发展的战略，以控制催化剂的选择性的基础上，无论是基板催化剂或离子催化剂的相互作用。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检查配对，以阐明离子控制催化的设计原理。这些适应性强的“响应催化剂”将允许探索非共价控制催化的新概念。该研究将为改进催化剂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。

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.