CAS: Organometallic Chemistry of High- and Low-Valent Nickel Centers

CAS：高价和低价镍中心的有机金属化学

• 批准号: 2155160
• 负责人: Liviu Mirica
• 金额: $ 52.5万
• 依托单位: University of Illinois at Urbana-Champaign
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-08-01 至 2025-07-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2155160&HistoricalAwards=false
• 关键词: CAS; Organometallic; Chemistry; Low; Valent

With the support of the Chemical Synthesis program in the Division of Chemistry, Professor Liviu M. Mirica of the Department of Chemistry at the University of Illinois at Urbana-Champaign (UIUC) will study the electronic properties and reactivity profiles of uncommon but reactive complexes of nickel that help in the production of useful organic compounds. The proposed studies will include a combination of synthetic chemistry to make the compounds and advanced spectroscopy for the characterization of these compounds, and thus will provide students in the research laboratory an interdisciplinary training and the opportunity to develop a broad range of scientific skills. In addition, Professor Mirica has developed a collaboration with Michael Webb from the neighboring Illinois State University (ISU) that will allow students from ISU to visit Professor Mirica’s laboratory for research and advanced spectroscopy studies. The PI will continue to be active in recruiting and training graduate and undergraduate students from different backgrounds, and will participate in the Chemistry Community program at UIUC aimed at increasing graduation rates for STEM (science, technology, engineering and mathematics) majors from underrepresented groups.It is well-known that palladium (Pd)-based complexes feature prominently as catalysts for cross-coupling reactions to generate C-C and C-X bonds. Nickel (Ni)-based systems have been recently developed given their generally broader substrate scope. This project by Professor Mirica deals with detailing the role of paramagnetic organometallic Ni complexes in important chemical transformations such as C-C and C-heteroatom bond formation and coupling. The project builds on Professor Mirica’s recent work in this area of chemistry of Ni chemistry, and will pursue the synthesis, isolation, detailed characterization, and reactivity studies of a series of organometallic Ni(III) complexes supported by flexible multidentate ligands. Novel organometallic Ni complexes in varied oxidation states will be isolated, characterized, and employed in new photocatalytic cross-coupling transformations. Professor Mirica and his group will investigate the photochemical and thermal reactivity of these Ni systems in detail, using the appreciable number of isolated organometallic Ni(III) and Ni(I) complexes expected to be synthesized in this project. The interdisciplinary training of students will span inorganic, organic, organometallic, and physical chemistry.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.

在化学系化学合成项目的支持下，Liviu M.伊利诺伊大学厄巴纳-香槟分校（UIUC）化学系的Mirica将研究镍的不常见但反应性络合物的电子性质和反应性特征，这些络合物有助于生产有用的有机化合物。拟议的研究将包括合成化学的组合，使这些化合物的化合物和先进的光谱表征，从而将为学生提供研究实验室的跨学科培训和发展广泛的科学技能的机会。此外，Mirica教授还与邻近的伊利诺伊州立大学（ISU）的Michael Webb合作，允许ISU的学生访问Mirica教授的实验室进行研究和高级光谱学研究。PI将继续积极招募和培训来自不同背景的研究生和本科生，并将参与UIUC的化学社区计划，旨在提高STEM的毕业率。（科学、技术、工程和数学）专业，来自代表性不足的群体。众所周知，钯（Pd）基配合物作为交叉偶联反应的催化剂，以产生C-C和C-X债券。镍（Ni）基系统最近已经被开发，因为它们通常具有更宽的基底范围。Mirica教授的这个项目详细介绍了顺磁性有机金属Ni络合物在重要化学转化中的作用，如C-C和C-杂原子键的形成和耦合。该项目建立在Mirica教授最近在Ni化学领域的工作基础上，将对一系列由柔性多齿配体支持的有机金属Ni（III）配合物进行合成，分离，详细表征和反应性研究。新颖的有机金属镍配合物在不同的氧化态将被分离，其特征在于，并采用新的光催化交叉耦合转换。Mirica教授和他的团队将详细研究这些Ni系统的光化学和热反应性，使用预计将在该项目中合成的大量孤立的有机金属Ni（III）和Ni（I）络合物。该奖项反映了NSF的法定使命，并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，被认为值得支持。

项目成果

Nickel–Carbon Bond Oxygenation with Green Oxidants via High-Valent Nickel Species

通过高价镍物质与绿色氧化剂进行镍-碳键氧化

• DOI: 10.1021/jacs.3c01012
• 发表时间: 2023
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Hu, Chi-Herng;Kim, Seoung-Tae;Baik, Mu-Hyun;Mirica, Liviu M.
• 通讯作者: Mirica, Liviu M.