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.

在化学系化学催化项目的支持下，弗吉尼亚大学的 T. Brent Gunnoe 教授将研究开发新型催化剂，将天然气和石油衍生的化学品转化为增值产品。化学工业的许多起始材料是来自化石来源（主要是天然气和石油）的碳氢化合物，必须通过化学方法将其转化为更高价值的材料。化学工业在这一过程中的能源消耗量很大，约占全球能源使用总量的 10%，占全球二氧化碳排放量的 5% 以上。虽然有机会大幅提高大规模化学过程的能源效率，但实现这一目标也面临着巨大的科学挑战。在这个项目中，Gunnoe 教授的团队旨在对如何进行选择性和节能的催化化学转化形成全新的理解，这对于以更环保的方式使用天然气和其他化石资源的目标至关重要。该项目将为 Gunnoe 教授与主要本科院校 (PUI) 合作奠定基础，扩大一项计划，以提高不同背景的学生对科学家和工程师职业的兴趣，特别是在能源领域。在这个项目中，研究生将访问 PUI，根据他们的研究提供短期课程，本科生将参加 Gunnoe 教授实验室的暑期研究实习。在化学系化学催化项目的支持下，弗吉尼亚大学的 T. Brent Gunnoe 教授将研究开发新型催化剂，将天然气和石油中的化学品转化为更高价值的产品。该项目将重点开发基于 Co、Rh、Ir 和 Pt 的新型催化剂，用于碳氢化合物（芳烃、烷烃和烯烃）的功能化。一个关键目标是加深对配体设计的基本理解，以控制实现有效 C-H 官能化所需的氧化还原化学，特别是在酸性介质等氧化条件下。这一广泛的目标是通过两个主要目标来实现的：(i) 了解“封端芳烃”配体对氧化还原反应的影响，包括使用 Co、Rh 和 Ir 络合物的催化烃氧化。 Gunnoe小组将量化封端芳烃配体结构，包括芳烃功能性以及“封端芳烃”基团相对于过渡金属和芳烃取代​​基的定位，如何影响应用于催化烯烃氢化、烯烃氧化以及碳氢化合物C-H活化和功能化的基于金属的氧化还原转化； (ii) 了解新型 Z 型配体对氧化还原反应的影响，包括使用 Rh、Ir 和 Pt 配合物催化 C-H 活化和功能化。 Gunnoe 小组将确定 Sb 基团控制过渡金属电子结构、将反应基团往返于过渡金属以及与过渡金属协同直接活化碳氢化合物底物的能力。这些研究将应用于催化碳氢化合物C-H官能化。这些努力的目标成果是加深对配体设计的理解，以优化 C-H 活化速率，特别是在酸性介质等氧化条件下，开发金属配位烯烃氧化官能化的新策略和工艺，并获得用于 C-H 官能化的新催化剂，包括使用空气可回收氧化剂部分氧化碳氢化合物。该奖项反映了 通过使用基金会的智力价值和更广泛的影响审查标准进行评估，NSF 的法定使命被认为值得支持。

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