Reactive Intermediates, Reaction Mechanisms, and Catalytic Cycles in the Gas Phase

反应中间体、反应机理和气相催化循环

• 批准号: 1565852
• 负责人: Mohamed Samy El-Shall
• 金额: $ 38万
• 依托单位: Virginia Commonwealth University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-05-01 至 2021-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1565852&HistoricalAwards=false
• 关键词: Reactive; Intermediates; Reaction; Mechanisms; Catalytic

The Chemical Structure, Dynamics and Mechanism Program of the NSF Chemistry Division supports the research of Professor Scott Gronert in the Department of Chemistry at Virginia Commonwealth University. Professor Gronert and his students are developing and using novel gas-phase techniques to study catalytic reactions that are important in the synthesis and production of pharmaceuticals and other fine chemicals. Their methodologies involve converting mass spectrometers into gas-phase reactors, and allow them to probe individual steps in complex reaction processes, with the goal of finding ways to improve the efficiency and selectivity of current catalysts. Professor Gronert and his group are also using this technology to seek out new catalytic systems that have superior properties to those currently in use. Professor Gronert's research program is deeply engaged in training students at all levels and encourages undergraduates to participate in independent research projects early in their college careers. In addition, Professor Gronert recruits one student each summer from a local HBCU (historically black college or university) to participate in a research project. The exceptional versatility of modern mass spectrometry offers unique opportunities for studying reactive intermediates under highly-controlled conditions and probing their intrinsic reactivity. The Gronert group has converted ion-trap mass spectrometers into ion reactors and uses them to study gas-phase reaction kinetics and equilibria. A central focus of the research involves isolating and characterizing key reactive intermediates in important catalytic cycles. In this project, three systems involving ligated metal complexes are being investigated: (1) The scope of new phenanthroline-based iridium(III) C-H activation catalysts; (2) New, 2-electron reduction methodologies to generate potential intermediates in cobalt- and nickel-catalyzed C-C coupling reactions; and (3) New 1-electron reduction methodologies to generate transition metals in unusual oxidation states and characterize their roles in reaction processes. In addition, a variable temperature ion reactor are being used to examine enthalpy/entropy effects in templated, gas-phase reaction systems. The outreach plan is tightly integrated into the research and a key component involves recruiting students each year from a local historically black university, Virginia Union University.

NSF化学部的化学结构，动力学和机制计划支持弗吉尼亚联邦大学化学系的Scott Gronert教授的研究。 Gronert教授和他的学生正在开发并使用新型的气相技术来研究在制药和其他精细化学物质的合成和生产中很重要的催化反应。 他们的方法涉及将质谱器转化为气相反应器，并允许它们在复杂的反应过程中探测单个步骤，以寻找提高当前催化剂的效率和选择性的方法。 Gronert教授和他的小组也正在使用这项技术来寻找与当前使用的催化系统相比具有优越性的催化系统。 格罗纳特教授的研究计划深入研究各个级别的学生，并鼓励大学生在大学职业生涯的早期就参与独立研究项目。 此外，每年夏天，格罗纳特教授从当地的HBCU（历史悠久的黑人学院或大学）招募一名学生参加研究项目。现代质谱法的特殊性具有特殊性，为在高度控制条件下研究反应性中间体并探测其内在反应性提供了独特的机会。 Gronert组已将离子陷阱质谱仪转化为离子反应器，并使用它们来研究气相反应动力学和平衡。 该研究的主要重点是隔离和表征重要的催化循环中的关键反应性中间体。 在该项目中，正在研究涉及连接金属络合物的三个系统：（1）新的基于苯〜thytarththroline的虹膜（III）C-H活化催化剂的范围； （2）新的2电子还原方法，以在钴和镍催化的C-C偶联反应中产生潜在的中间体； （3）新的1电子还原方法，以在异常氧化状态下产生过渡金属并表征其在反应过程中的作用。 另外，正在使用变化的温度离子反应器来检查模板的气相反应系统中的焓/熵效应。 宣传计划紧密整合到研究中，关键组成部分涉及每年从当地历史悠久的黑人大学弗吉尼亚联合大学招募学生。