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RUI: Mechanistic Studies of Ruthenium-Catalyzed Ester Hydrogenation

RUI：钌催化酯加氢反应机理研究

基本信息

批准号：
1954924
负责人：
Anthony Chianese
金额：
$ 33.56万
依托单位：
Colgate University
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2020
资助国家：
美国
起止时间：
2020-09-01 至 2024-08-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1954924&HistoricalAwards=false
关键词：
RUI Mechanistic Studies Ruthenium Catalyzed

项目摘要

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.

凭借这一奖项，美国国家科学基金会化学部的化学催化项目正在支持科尔盖特大学的Anthony Chianese教授和Jason Keith教授的研究，以了解催化剂在分子水平上如何在称为酯氢化的化学过程中起作用。在化学工业中，这种反应经常在高温和高压氢气下大规模进行。化学催化领域的一个主要目标是发展有效的工艺，尽量减少危险废物的产生，并在节能条件下操作。中国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。这些研究有助于提高基础科学知识，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本科生在科尔盖特大学的研究实验室进行的。参与本科生研究，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受到认可。每年夏天，中国教授和他研究小组的学生们还会抽出一天时间，为参加“第五营”（Camp five）的高中生开展一项拓展活动。“第五营”是一个住宿夏令营，接待一群来自纽约市和纽约州北部农村地区的高危学生。在之前由美国国家科学基金会资助的一个项目中，中国教授和基思教授发现，他们实验室开发的钌配合物，以及一种被广泛使用的钌配合物米尔斯坦催化剂，经历了不可逆的化学转化，成为酯氢化的活性催化剂。这一发现对先前提出的米尔斯坦催化剂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提出了质疑。在目前的项目中，中国和基思正在进行详细的实验和计算研究，以准确地了解米尔斯坦的催化剂是如何在分子水平上起作用的。该项目利用了中国在实验力学研究方面的专业知识和Keith在反应机理计算分析方面的专业知识。这些研究的目的之一是确定无活性的钌预催化剂如何转化为具有催化活性的形式。另一个目的是了解与这些配合物形成酯氢化催化循环的单个化学反应。收集这些知识是为了帮助合理开发用于酯加氢和相关过程的改进催化剂。该项目还为本科生提供了宝贵的培训，并为处于危险中的高中生提供了接触化学研究的机会。该奖项反映了美国国家科学基金会的法定使命，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。