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.

在化学合成计划中的支持下，伊利诺伊大学Urbana-Champaign（UIUC）化学系的Liviu M. Mirica教授将研究镍的不寻常但反应性复合物的电子性能和反应性曲线，有助于产生有用的有机化合物的产生。拟议的研究将包括合成化学的结合，以使化合物和高级光谱法以表征这些化合物，从而为研究实验室中的学生提供跨学科的培训以及开发广泛的科学技能的机会。此外，Mirica教授与邻近伊利诺伊州立大学（ISU）的迈克尔·韦伯（Michael Webb）建立了合作，该大学将允许ISU的学生访问Mirica教授的研究和高级光谱研究。 PI将继续积极参与来自不同背景的招聘和培训研究生和本科生，并将参加UIUC的化学社区计划，旨在提高STEM（科学，技术，技术，工程和数学）专业的毕业率，来自代表性不足的群体。 C-X键。鉴于其通常更广泛的底物范围，最近已经开发了基于镍（NI）的系统。 Mirica教授的该项目介绍了详细介绍顺磁性有机Ni复合物在重要化学转化中的作用，例如C-C和C-杂质键形成和耦合。该项目建立在Mirica教授在NI化学化学领域的最新研究，并将追求一系列由柔性多层配体支持的有机NI（III）复合物的合成，隔离，详细表征和反应性研究。在新的光催化交叉偶联转化中，将分离，表征和执行各种氧化态中新型的有机Ni复合物。 Mirica教授和他的小组将详细研究这些NI系统的光化学和热反应性，使用可在本项目中合成预计将合成的隔离有机Ni（III）和Ni（I）配合物。对学生的跨学科培训将涵盖无机，有机，有机和物理化学的培训。该奖项反映了NSF的法定任务，并通过使用基金会的知识分子优点和更广泛的影响评估标准来评估，被认为是珍贵的支持。

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.