LEAPS-MPS: Topological Control of Ligand Hemilability in Organometallic Nickel Complexes for C-H Activation

LEAPS-MPS：用于 C-H 活化的有机金属镍配合物中配体半稳定性的拓扑控制

• 批准号: 2316849
• 负责人: Nathanael Hirscher
• 金额: $ 24.92万
• 依托单位: Montclair State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-09-15 至 2025-08-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2316849&HistoricalAwards=false
• 关键词: LEAPS; MPS; Topological; Control; Ligand

In this project funded by the Chemistry Division at NSF, Professor Nathanael Hirscher and his students at Montclair State University will perform studies that aim to develop new catalysts resulting in increased rates and durability for important reactions relevant to chemical manufacturing. This research will combine organic components (ligands) with a metal (nickel) to make organometallic complexes. The structure of the organic ligand strongly influences the properties of the organometallic complex. Breaking carbon-hydrogen bonds (i.e., C-H activation) is an important step in organometallic catalysis, with applications in the production of pharmaceuticals and polymers. Professor Hirscher and his students will synthesize ligands with varying structures, as well as complexes comprised of the ligands and nickel. Their studies could improve the ability of nickel complexes to perform C-H activation by precise control of peripheral elements in the ligand. In addition, students from diverse backgrounds, including those from underrepresented minority groups, will be trained in organometallic chemistry and mentored as part of a cohort of undergraduates in chemistry research at Montclair State University.This work is an endeavor to improve organometallic catalysis by applying strategies from supramolecular chemistry. Breaking carbon-hydrogen bonds (C-H activation) is a crucial step in catalysis technology, significant to the production of chemicals ranging from pharmaceuticals to polymers. The ability of nickel complexes to perform C-H activation will be studied in this work. Organometallic chemistry has traditionally focused on the interaction between metals and organic ligands, but the peripheral parts of the structure (i.e., the secondary coordination sphere) have attracted much recent attention. This project involves the exploration of a specific aspect of the secondary coordination sphere: the interconnectivity (i.e., topology) of ligand structural features within an organometallic complex. Nickel complexes will be synthesized and studied to determine whether the topology of the ligand influences C-H activation. More specifically, the influence of hemilabile donors within the ligand secondary structure will be studied, regarding their impact on C-H activation rates of the nickel complexes.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.

在由NSF化学部资助的该项目中，Nathanael Hirscher教授及其蒙特克莱州立大学的学生将进行研究，旨在开发新的催化剂，从而提高与化学制造相关的重要反应的速率和耐用性。这项研究将将有机成分（配体）与金属（镍）结合起来，以制成有机金属络合物。有机配体的结构强烈影响有机金属络合物的特性。破坏碳 - 氢键（即C-H激活）是有机金属催化的重要一步，在制药和聚合物的生产中应用。 Hirscher教授和他的学生将通过不同的结构以及由配体和镍组成的建筑物合成配体。他们的研究可以通过精确控制配体中的外围元素来提高镍复合物执行C-H激活的能力。此外，来自不同背景的学生，包括来自代表性不足的少数群体的学生，将接受有机金属化学的培训，并作为蒙特克莱州立大学化学研究的一系列本科生的指导，这是一项工作。这项工作是通过从超核分泌型化学中应用有机金属催化策略来改善有机金属催化的工作。破坏碳 - 氢键（C-H激活）是催化技术的关键步骤，对于从药物到聚合物的化学物质的产生意义。在这项工作中将研究镍复合物执行C-H激活的能力。传统上，有机金属化学集中在金属和有机配体之间的相互作用上，但是结构的周围部分（即二级配位球体）吸引了最近的关注。该项目涉及探索次级协调领域的特定方面：有机金属络合物内配体结构特征的互连（即拓扑）。镍配合物将进行合成和研究，以确定配体的拓扑是否会影响C-H激活。更具体地说，将研究Hemilabile供体在配体二级结构中的影响，这些奖项反映了NSF的法定任务，这反映了NSF的法定任务，并被认为是值得通过基金会的智力优点和更广泛的影响审查标准来评估的。