RUI: Mechanistic Studies of Ruthenium-Catalyzed Ester Hydrogenation

有了这个奖项，NSF化学部的化学催化计划正在支持Colgate大学的Anthony Chianese教授和Jason基思教授的研究，以了解催化剂如何在分子水平上运行，用于称为酯氢化的化学过程。该反应在化学工业中以非常大的规模进行，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，并在节能条件下运行。Chianese和基思正在使用实验室和计算机模拟相结合的方法来确定最知名的酯加氢催化剂是如何工作的。这些研究为基础科学知识做出了贡献，并有助于设计下一代改进的催化剂。该项目的所有研究都是由本科生在高露洁大学的研究实验室进行的。参与本科研究，特别是在学生职业生涯的早期，越来越多地认识到其对学生的积极影响，并扩大参与科学。奇尼斯教授和他的研究小组的学生们每年夏天都会花一天时间为参加五号营的高中生举办一次外展活动。五号营是一个寄宿夏令营，在纽约市和纽约州北部的农村地区，有一群高危学生参加。在之前的一个由美国国家科学基金会资助的项目中，奇尼斯教授和基思教授发现，钌络合物是在他们的实验室里形成的，以及广泛使用的称为Milstein催化剂的钌络合物，经历不可逆的化学转化而成为酯氢化的活性催化剂。这一发现对先前提出的Milstein催化剂如何促进酯氢化的机制提出了质疑，以及广泛的相关氢化和极性键的取代。在目前的项目中，Chianese和基思正在进行一项详细的实验和计算研究，以准确了解Milstein的催化剂在分子水平上是如何运作的。这个项目借鉴了中国人在实验机理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涉及确定非活性钌预催化剂如何转化成其催化活性形式。另一个目标是了解组成这些络合物酯氢化催化循环的各个化学反应。正在收集这些知识，以协助合理开发酯氢化和相关工艺的改进催化剂。该计划还为本科生提供了宝贵的培训，并为处于风险中的高中生提供了了解化学研究的机会。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 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.