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.

在这个由NSF化学部资助的项目中，州立大学蒙特克莱尔的Nathanael Hirscher教授和他的学生将进行研究，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久性。本研究将联合收割机有机成分（配体）与金属（镍）结合，制成有机金属配合物。有机配体的结构强烈影响有机金属配合物的性质。打破碳-氢键（即，C-H活化）是有机金属催化中的重要步骤，在药物和聚合物的生产中具有应用。Hirscher教授和他的学生将合成具有不同结构的配体，以及由配体和镍组成的络合物。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配合物进行C-H活化的能力。此外，来自不同背景的学生，包括那些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，并作为蒙特克莱尔州立大学化学研究本科生的一部分进行指导。这项工作是通过应用超分子化学的策略来改善有机金属催化的奋进。打破碳-氢键（C-H活化）是催化技术的关键步骤，对从药物到聚合物的化学品的生产具有重要意义。本工作将研究镍配合物进行C-H活化的能力。有机化学传统上关注金属和有机配体之间的相互作用，但结构的外围部分（即，次级协调领域）最近引起了很大的注意。该项目涉及探索次级协调领域的一个具体方面：互联性（即，拓扑结构）的有机金属配合物内配体结构特征。镍配合物将被合成和研究，以确定是否拓扑结构的配体影响C-H活化。更具体地说，半不稳定的捐助者内的配体二级结构的影响将进行研究，关于其对C-H活化率的镍complex.This奖的影响反映了NSF的法定使命，并已被认为是值得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的支持。