Ligand Controlled Redox Catalysis with Late Transition Metal Complexes

后过渡金属配合物配体控制的氧化还原催化

• 批准号: 2102433
• 负责人: Thomas Gunnoe
• 金额: $ 50万
• 依托单位: University of Virginia Main Campus
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-08-01 至 2024-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2102433&HistoricalAwards=false
• 关键词: Ligand; Controlled; Redox; Catalysis; Late

With support from the Chemical Catalysis program in the Division of Chemistry, Professor T. Brent Gunnoe of the University of Virginia will study the development of new catalysts for the conversion of chemicals derived from natural gas and petroleum into value-added products. Many starting materials for the chemical industry are hydrocarbons derived from fossil sources (primarily natural gas and petroleum), which must be chemically converted into higher value materials. The chemical industry's energy consumption for this process is substantial and accounts for approximately 10% of total global energy use and greater than 5% of global carbon dioxide emissions. While there are opportunities to dramatically increase the energy efficiency of large-scale chemical processes, there are also substantial scientific challenges to realizing this goal. In this project, Professor Gunnoe's group aims to develop a fundamentally new understanding of how to perform selective and energy-efficient catalytic chemical transformations that are essential to the goal of using natural gas and other fossil resources in a more environmentally benign manner. The project will provide a foundation for Professor Gunnoe to work with primarily undergraduate institutions (PUIs) to expand a program to increase interest among students from diverse backgrounds in careers as scientists and engineers, especially in the energy arena. In this program, graduate students will visit PUIs to deliver short courses based on their research, and undergraduate students will participate in summer research internships in Professor Gunnoe's laboratory. With support from the Chemical Catalysis program in the Division of Chemistry, Professor T. Brent Gunnoe of the University of Virginia will study the development of new catalysts for the conversion of chemicals derived from natural gas and oil into higher value products. The project will focus on the development of new catalysts, based on Co, Rh, Ir and Pt for the functionalization of hydrocarbons (arenes, alkanes and olefins). A key goal will be to advance a fundamental understanding of ligand design to control redox chemistry necessary to achieve efficient C–H functionalization, especially under oxidizing conditions such as acidic media. This broad goal is to be achieved through two primary objectives: (i) to understand the impact of "capping arene" ligands on redox reactions, including catalytic hydrocarbon oxidation, using Co, Rh and Ir complexes. The Gunnoe group will quantify how the capping arene ligand structure, including arene functionality and positioning of "capping arene" group relative to the transition metal and arene substituents, impacts metal-based redox transformations as applied to catalytic olefin hydrogenation, olefin oxidation, and hydrocarbon C–H activation and functionalization; and (ii) to understand the effect of new Z-type ligands on redox reactions, including catalytic C–H activation and functionalization, using Rh, Ir and Pt complexes. The Gunnoe group will determine the ability of the Sb group to control transition metal electronic structure, shuttle reactive groups to/from the transition metal, and to directly activate hydrocarbon substrates in concert with the transition metal. These studies will be applied to catalytic hydrocarbon C–H functionalization. The targeted outcome of these efforts is to gain an improved understanding of ligand design to optimize rates of C–H activation, especially under oxidizing conditions such as in acidic media, to develop new strategies and processes for the oxidative functionalization of metal-coordinated olefins, and to access new catalysts for C–H functionalization, including partial oxidation of hydrocarbons using air-recyclable oxidants.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.

在化学催化计划中的化学催化计划的支持下，弗吉尼亚大学的T. Brent Gunnoe教授将研究新的催化剂的开发，以转化源自天然气和石油为增值产品的化学物质。化学工业的许多起始材料都是源自化石源（主要是天然气和石油）的碳氢化合物，必须将其化学转化为更高的价值材料。化学工业在这一过程中的能源消耗是实质性的，约占全球总能源使用的10％，大于全球二氧化碳排放量的5％。尽管有机会大大提高大型化学过程的能源效率，但实现这一目标也存在重大的科学挑战。在这个项目中，Gunnoe教授的小组旨在对如何进行选择性和节能的催化化学转化进行基本的新了解，这对于以更环保的方式使用天然气和其他化石资源至关重要。该项目将为Gunnoe教授与小学本科机构（PUI）合作，为扩大计划，以增加来自科学家和工程师，尤其是能源领域的科学家和工程师的学生的兴趣。在该计划中，研究生将根据他们的研究来访问PUI，以提供简短的课程，本科生将参加Gunnoe教授实验室的夏季研究实习。在化学催化计划中的化学催化计划的支持下，弗吉尼亚大学的T. Brent Gunnoe教授将研究开发新催化剂，以转化从天然气和石油到更高价值产品的化学品转化。该项目将集中于基于CO，RH，IR和PT的新催化剂的开发，用于碳氢化合物的功能化（Arenes，Alkanes和Olefins）。一个关键目标是提高对配体设计的基本理解，以控制实现有效C – H功能化所需的氧化还原化学，尤其是在氧化条件下（例如酸性培养基）。这个广泛的目标是通过两个主要对象来实现：（i）使用CO，RH和IR复合物了解“限制芳烃”配体对氧化还原反应的影响，包括催化碳氢化合物氧化物。 Gunnoe组将量化限制的芳烃配体结构，包括芳烃功能和“封盖芳烃”基团相对于过渡金属和芳香烯烃的定位，会影响基于金属的氧化还原转化，以应用于催化烯烃氢化，烯烃氧化，烯烃C – H活化和功能化； （ii）使用RH，IR和PT复合物了解新的Z型配体对氧化还原反应的影响，包括催化C – H的激活和功能化。 Gunnoe组将确定SB组控制过渡金属电子结构的能力，从过渡金属进行反应性基团，并直接与过渡金属一起激活碳氢化合物底物。这些研究将应用于催化烃C – H功能化。这些努力的有针对性结果是，对配体设计有了深入的了解，以优化C – H激活的速率，尤其是在诸如酸性培养基等氧化条件下，以开发新的策略和过程，以氧化金属配位烯烃的氧化功能化，并访问CO型氧化能力的新催化剂，包括使用氧化氧化的促氧化剂，包括水合氧化的氧化氧化剂，并将其氧化。 NSF的法定使命，并使用基金会的知识分子优点和更广泛的影响审查标准来评估值得支持。

项目成果

Capping Arene Ligated Rhodium-Catalyzed Olefin Hydrogenation: A Model Study of the Ligand Influence on a Catalytic Process That Incorporates Oxidative Addition and Reductive Elimination

封端芳烃连接铑催化烯烃氢化：配体对氧化加成和还原消除催化过程影响的模型研究

• DOI: 10.1021/acs.organomet.2c00317
• 发表时间: 2022
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Zhang, Ke;Musgrave, Charles B.;Dickie, Diane A.;Goddard, William A.;Gunnoe, T. Brent
• 通讯作者: Gunnoe, T. Brent