RUI: Improving Activity and Selectivity in Ruthenium-Catalyzed Hydrogenation Reactions Through Mechanistic Understanding

RUI：通过机理理解提高钌催化氢化反应的活性和选择性

• 批准号: 2247229
• 负责人: Anthony Chianese
• 金额: $ 36万
• 依托单位: Colgate University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-09-01 至 2026-08-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2247229&HistoricalAwards=false
• 关键词: RUI; Improving; Activity; Selectivity; Ruthenium

With support from the Chemical Catalysis Program in the Division of Chemistry, Anthony Chianese and Jason Keith of Colgate University are studying how catalysts operate at a molecular level to improve their efficiency and sustainability. A major goal in chemistry is the development of sustainable chemical reactions that minimize the production of hazardous waste and operate under energy-efficient conditions. The co-principal investigators (co-PIs), Drs. Chianese and Keith, are using a combined experimental- and computer-modeling-based approach to elucidate the mechanisms of catalysts for the epoxide hydrogenolysis reaction. While this is an important reaction in the pharmaceutical and chemical industries, current methods for this reaction produce significant amounts of hazardous waste, which limits the sustainability of the process. Replacing traditional chemical reagents with hydrogen gas has the potential to significantly reduce the reaction’s cost and environmental impact. Understanding how the reaction works at a microscopic level would contribute basic scientific knowledge and facilitate the design of the next generation of improved catalysts. The research for this project is being conducted by undergraduate students in the laboratories of the PIs at Colgate University. Participation in undergraduate research, especially early in a student’s career, is increasingly recognized for its positive impacts on students and for broadening participation in the sciences. Chianese and the students working in his research group devote a day each summer to 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 previous NSF-funded research, PIs Chianese and Keith used a combined experimental/computational approach to determine the mechanism of ester hydrogenation catalyzed by a widely used complex, Milstein’s catalyst, and showed how the catalyst converts from its original form to the form active in catalytic hydrogenation reactions. In the current project, Chianese and Keith are applying this knowledge to a new transformation, the ruthenium-catalyzed hydrogenolysis of epoxides. The project aims to develop highly active catalysts for epoxide hydrogenolysis that are selective for one isomer of the product alcohol, and to understand how these catalysts operate at the molecular level. In another thrust, the Chinese-Keith research team will revisit the previously proposed mechanisms of related hydrogenation reactions promoted by Milstein’s catalyst, building on their recent discovery that Milstein’s catalyst irreversibly transforms upon heating to a different form with a catalytically relevant hydrogen bound to a nitrogen atom. This project has the potential to result in new, more sustainable chemical transformations, and to improve our understanding of how these reactions proceed at a molecular level.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.

在化学系化学催化项目的支持下，高露洁大学的Anthony Chianes和Jason Keith正在研究催化剂如何在分子水平上运行，以提高其效率和可持续性。化学的一个主要目标是发展可持续的化学反应，最大限度地减少危险废物的产生，并在节能的条件下运行。联席首席研究员钱恩斯博士和基思博士正在使用实验和计算机模拟相结合的方法来阐明催化剂对环氧化物氢解反应的机理。虽然这在制药和化学工业中是一种重要的反应，但目前这种反应的方法会产生大量的危险废物，这限制了该过程的可持续性。用氢气取代传统的化学试剂有可能显著降低反应成本和对环境的影响。了解反应在微观水平上的工作原理将有助于提供基本的科学知识，并有助于设计下一代改进的催化剂。这个项目的研究是由高露洁大学PI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。基亚尼斯和他的研究小组的学生每年夏天都会花一天时间为参加第五营的高中生举办一项外展活动，这是一个寄宿夏令营，接待了一群高危学生，包括纽约市和纽约州北部的农村。在之前由美国国家科学基金会资助的研究中，皮斯基亚尼斯和基思使用实验/计算相结合的方法来确定被广泛使用的络合物-米尔斯坦催化剂催化的酯加氢机理，并展示了催化剂如何从原来的形式转化为催化加氢反应中活跃的形式。在目前的项目中，基恩斯和基思正在将这一知识应用于一种新的转化，即Ru催化的环氧化物氢解。该项目旨在开发对产物醇的一种异构体具有选择性的高活性环氧化物氢解催化剂，并了解这些催化剂在分子水平上的工作原理。在另一个推力中，中国和基思的研究团队将重新审视之前提出的由米尔斯坦的催化剂促进的相关氢化反应的机制，基于他们最近的发现，米尔斯坦的催化剂在加热后不可逆转地转化为不同的形式，与催化相关的氢原子与氮原子结合。该项目有可能导致新的、更可持续的化学转化，并提高我们对这些反应如何在分子水平上进行的理解。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。