CAREER: Dynamic Hemilability Controlled by Cation-Responsive Pincer-crown Ether Catalysts

事业：由阳离子响应钳冠醚催化剂控制的动态半稳定性

• 批准号: 1553802
• 负责人: Alexander Miller
• 金额: $ 67.5万
• 依托单位: University of North Carolina at Chapel Hill
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-05-01 至 2022-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1553802&HistoricalAwards=false
• 关键词: CAREER; Dynamic; Hemilability; Controlled; Cation

In this project funded by the Chemical Catalysis Program of the Chemistry Division, Professor Alexander Miller of the Department of Chemistry at the University of North Carolina at Chapel Hill is developing cation-responsive catalysts for the sustainable synthesis of chemical building blocks. Catalysts are vital in many industrial and laboratory chemical processes. Many catalysts involve a metal atom that contains a reactive center that can facilitate chemical reactions. However, this reactive center, itself, can be prone to reactions that can deactivate it. This project involves the development of ligands (groups that are attached to a metal) that contain one portion that is firmly bonded to the metal and another that can be relatively easily removed from the metal to open a reactive site. These ligands are called hemilabile ligands. The hemilabile ligands targeted contain a group that can bind to an external positive ion that remove that group from the metal. This permits a balance of activity and stability that advances catalysis relevant to the pharmaceutical and commodity chemical industries. The educational approach focuses on communication in chemistry. Graduate students are participating in a science communication initiative in collaboration with a local science center, the Morehead Planetarium, creating hands-on activities that illustrate the role of catalysis in everyday life. The Safety Net is also being established as an online network of safety resources to encourage communication between academic and industrial scientists. The research approach utilizes new "pincer-crown ether" ligands that contain a macrocylic cation receptor site to modulate reactivity. Mechanistic studies are establishing the parameters that allow cations to tune individual organometallic reactions steps, supporting the development of catalysts that exhibit distinct activity and selectivity in the presence of various cations. The combined education and research program is training graduate students in catalysis research, safe laboratory practices, and science communication with the public.

在这项由化学系化学催化计划资助的项目中，北卡罗来纳大学教堂山分校化学系的亚历山大·米勒教授正在开发阳离子响应型催化剂，用于可持续合成化学构建块。催化剂在许多工业和实验室化学过程中是至关重要的。许多催化剂都包含一个金属原子，该原子含有一个可以促进化学反应的反应中心。然而，这个反应中心本身很容易发生使其失活的反应。该项目涉及开发配体(连接到金属上的基团)，这种配体包含牢固地结合到金属上的一部分，以及可以相对容易地从金属上移除以打开反应位置的另一部分。这些配体被称为半活性配体。目标半疏水配体包含一个基团，该基团可以与外部阳离子结合，从而将该基团从金属上移除。这使得活性和稳定性达到平衡，从而促进了与制药和商品化学工业相关的催化作用。教育方法侧重于化学中的交流。研究生们正在参与一项与当地科学中心莫尔黑德天文馆合作的科学交流活动，创建实践活动，展示催化在日常生活中的作用。安全网也正在建立，作为一个安全资源的在线网络，以鼓励学术和工业科学家之间的交流。该研究方法利用含有大环阳离子受体位点的新的“钳形-冠醚”配体来调节反应活性。机理研究正在建立允许阳离子调节单个有机金属反应步骤的参数，支持开发在各种阳离子存在下表现出不同活性和选择性的催化剂。这一教育和研究相结合的项目正在培训研究生进行催化研究、安全实验室实践以及与公众进行科学交流。

项目成果

Selecting Double Bond Positions with a Single Cation-Responsive Iridium Olefin Isomerization Catalyst

• DOI: 10.1021/jacs.0c11601
• 发表时间: 2021-02-08
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Camp, Andrew M.;Kita, Matthew R.;Miller, Alexander J. M.
• 通讯作者: Miller, Alexander J. M.