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

在化学系化学合成项目的支持下，伊利诺伊大学厄巴纳-香槟分校（UIUC）化学系的Liviu M. Mirica教授将研究镍的电子性质和反应性特征，这些特征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来制造化合物和先进的光谱来表征这些化合物，因此将为研究实验室的学生提供跨学科的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的化学社区项目，旨在提高来自弱势群体的STEM（科学、技术、工程和数学）专业的毕业率。众所周知，钯基配合物在产生C-C和C-X键的交叉偶联反应中具有重要的催化剂作用。镍基系统由于其广泛的衬底范围而得到了最近的发展。Mirica教授的这个项目详细介绍了顺磁性有机金属Ni配合物在重要的化学转化中的作用，如C-C和c -杂原子键的形成和偶联。该项目建立在Mirica教授最近在Ni化学领域的工作基础上，并将进行一系列由柔性多齿配体支持的有机金属Ni（III）配合物的合成、分离、详细表征和反应性研究。不同氧化态的新型有机金属镍配合物将被分离、表征，并用于新的光催化交叉偶联转化。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，使用预计在该项目中合成的相当数量的分离有机金属Ni（III）和Ni(I)配合物。学生的跨学科训练将跨越无机、有机、有机金属和物理化学。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。

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.