CAS: Cu, Fe, and Ni Pincer Complexes: A Platform for Fundamental Mechanistic Investigations and Reaction Discovery

CAS：Cu、Fe 和 Ni 钳配合物：基础机理研究和反应发现的平台

• 批准号: 2349827
• 负责人: Melanie Sanford
• 金额: $ 79.31万
• 依托单位: Regents of the University of Michigan - Ann Arbor
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2024
• 资助国家: 美国
• 起止时间: 2024-05-01 至 2028-04-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2349827&HistoricalAwards=false
• 关键词: CAS; Cu; Fe; Ni; Pincer

With the support of the Chemical Catalysis program in the Division of Chemistry, Professor Melanie Sanford of the University of Michigan is studying catalysts derived from copper, nickel, and iron complexes. These metals are all earth abundant transition metals in contrast to metals such as palladium, rhodium and iridium that are often employed in traditional organometallic chemistry. This project aims to help build the scientific foundation needed to deploy inexpensive, earth abundant catalysts in C-H activation and elaboration chemistries, staple transformations of the chemical and pharmaceutical industries, ultimately enabling the replacement of costly and rare precious metals that currently dominate these industries. It will also provide interdisciplinary training to chemistry PhD students for careers in the STEM (science, technology, engineering and mathematics) workforce. Finally, it will support outreach efforts to engage Michigan middle and high-school students in the scientific process, specifically in hands-on electrochemistry activities (building voltaic piles), thereby encouraging them to become engaged in the future STEM workforce.Under this award, Professor Melanie Sanford and her team at the University of Michigan are studying Cu, Ni, and Fe pincer complexes as a platform for fundamental mechanistic investigations and reaction discovery. The proposed work will interrogate intermediates, pathways, and mechanisms in copper, nickel, and iron-catalyzed directed C–H bond functionalization reactions proceeding via LNC pincer-type intermediates. With all three metals, the mechanisms of cyclometalation and oxidative functionalization will be explored as a function of bidentate directing group, supporting ligands, and oxidant. Experimental approaches will focus on the isolation and/or detection of key intermediates, leveraging 19F NMR spectroscopy as a versatile tool for in situ monitoring of both diamagnetic and paramagnetic species. A key goal of this work is to achieve a deeper understanding of first-row transition-metal catalyzed C–H functionalization reactions, ultimately to inform the development of new catalytic transformations as well as broader applications of LNC pincer complexes in catalysis.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，密歇根大学的Melanie Sanford教授正在研究从铜、镍和铁络合物中提取的催化剂。与传统有机金属化学中经常使用的钯、铑和铱等金属相比，这些金属都是富含地球的过渡金属。该项目旨在帮助建立所需的科学基础，以在碳氢活化和精化化学、化学和制药工业的主要转化中部署廉价、含土丰富的催化剂，最终实现取代目前主导这些行业的昂贵和稀有贵金属。它还将为化学博士生在STEM（科学、技术、工程和数学）领域的职业生涯提供跨学科培训。最后，它将支持外联工作，使密歇根州的中学生和高中生参与科学过程，特别是在动手电化学活动（建立伏打桩）中，从而鼓励他们参与未来的STEM劳动力。在这个奖项下，密歇根大学的Melanie Sanford教授和她的团队正在研究Cu， Ni和Fe螯合物，作为基础机理研究和反应发现的平台。这项工作将探讨铜、镍和铁催化的定向C-H键功能化反应中的中间体、途径和机制，这些反应是通过LNC钳型中间体进行的。对于这三种金属，环金属化和氧化功能化的机制将作为双齿导向基团，支持配体和氧化剂的功能进行探索。实验方法将侧重于关键中间体的分离和/或检测，利用19F核磁共振波谱作为抗磁性和顺磁性物质原位监测的多功能工具。这项工作的一个关键目标是实现对第一行过渡金属催化的C-H功能化反应的更深入了解，最终为新的催化转化的发展以及LNC钳形配合物在催化中的更广泛应用提供信息。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。