RUI: Mechanistic Studies of Ruthenium-Catalyzed Ester Hydrogenation

通过这一奖项，美国国家科学基金会化学部的化学催化项目支持了高露洁大学的Anthony Chianes教授和Jason Keith教授的研究，以了解催化剂如何在分子水平上对称为酯加氢的化学过程进行操作。这种反应在化学工业中非常大规模地进行，通常在高温和高压氢气下进行。化学催化领域的一个主要目标是开发有效的工艺，最大限度地减少危险废物的产生，并在节能的条件下运行。基尼斯和基思正在使用实验室和计算机建模相结合的方法来确定最著名的酯加氢催化剂是如何运作的。这些研究正在为基础科学知识做出贡献，并有助于设计下一代改进的催化剂。这个项目的所有研究都是由高露洁大学研究实验室的本科生进行的。参与本科生的研究，特别是在学生职业生涯的早期，因其对学生的积极影响和扩大对科学的参与而日益得到认可。基亚尼斯教授和他的研究小组的学生每年夏天都会抽出一天时间，为参加五号营地的高中生举办一项外展活动，这是一个宿营夏令营，接待了一群处于危险之中的纽约市和纽约州北部乡村的学生。在之前由美国国家科学基金会资助的一个项目中，基亚尼斯教授和基思教授发现，在他们的实验室中形成的Ru络合物，以及一种被广泛使用的被称为米尔斯坦催化剂的Ru络合物，经历了不可逆转的化学转化，成为酯加氢的活性催化剂。这一发现质疑了之前提出的米尔斯坦催化剂如何促进酯氢化的机制，以及一系列相关的极性键的氢化和脱氢。在目前的项目中，基尼斯和基思正在进行一项详细的实验和计算研究，以准确地了解米尔斯坦的催化剂在分子水平上是如何运作的。这个项目利用了中国人在实验力学研究方面的专业知识和基思在反应机理计算分析方面的专业知识。这些研究的一个目的是确定非活性的Ru前催化剂如何转化为它们的催化活性形式。另一个目的是了解与这些络合物一起构成酯氢化催化循环的各个化学反应。正在收集这些知识，以帮助合理开发用于酯加氢的改进催化剂和相关工艺。该计划还为本科生提供了宝贵的培训，并为高危高中生提供了接触化学研究的机会。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 this award, the Chemical Catalysis Program of the NSF Division of Chemistry is supporting the research of Professors Anthony Chianese and Jason Keith at Colgate University to understand how catalysts operate at a molecular level for a chemical process called ester hydrogenation. This reaction is carried out on a very large scale in the chemical industry, often at high temperatures and under high pressures of hydrogen gas. A major goal in the field of chemical catalysis is the development of efficient processes that minimize the production of hazardous waste and operate under energy-efficient conditions. Chianese and Keith are using a combined laboratory and computer-modeling approach to determine how the best-known ester hydrogenation catalysts operate. These studies are contributing to basic scientific knowledge and helping to design the next generation of improved catalysts. All of the research for this project is being conducted by undergraduate students in the investigators' laboratories at Colgate University. Participation in undergraduate research, especially early in a student’s career, is increasingly recognized for its positive impact on students and for broadening participation in the sciences. Professor Chianese and the students working in his research group also devote a day each summer to running an outreach activity for high school students attending Camp Fiver, a residential summer camp that hosts a group of at-risk students New York City and rural upstate New York.In a previous NSF-funded project, Professors Chianese and Keith discovered that ruthenium complexes developed in their laboratory, as well as a widely used ruthenium complex known as Milstein’s catalyst, undergo an irreversible chemical transformation to become active catalysts for ester hydrogenation. This finding called into question previously suggested mechanisms for how Milstein’s catalyst promotes ester hydrogenation, as well as a wide array of related hydrogenations and dehydrogenations of polar bonds. In the current project, Chianese and Keith are undertaking a detailed experimental and computational study to understand precisely how Milstein’s catalyst operates at a molecular level. This project draws upon Chianese’s expertise in experimental mechanistic study and Keith’s expertise in computational analysis of reaction mechanisms. One aim of these studies involves determining how the inactive ruthenium precatalysts convert into their catalytically active forms. Another aim focuses on understanding the individual chemical reactions that make up the catalytic cycle for ester hydrogenation with these complexes. This knowledge is being collected to assist in the rational development of improved catalysts for ester hydrogenation and related processes. This program is also providing valuable training for undergraduate students and opportunities for at-risk high schools students to be introduced to chemical research.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.