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

在这个由NSF化学部资助的项目中，蒙特克莱尔州立大学的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用性。这项研究将有机成分(配体)与一种金属(镍)结合起来，形成有机金属络合物。有机配体的结构对有机金属络合物的性质有很大影响。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有着广泛的应用。赫舍尔教授和他的学生将合成不同结构的配体，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执行C-H活化的能力。此外，来自不同背景的学生，包括那些来自代表不足的少数群体的学生，将接受有机金属化学培训，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进有机金属催化的努力。打破碳氢键(C-H活化)是催化技术中的关键步骤，对从药物到聚合物的各种化学品的生产都具有重要意义。本工作将对镍配合物进行C-H活化的能力进行研究。有机金属化学传统上侧重于金属与有机配体之间的相互作用，但结构的外围部分(即二次配位球)最近引起了人们的极大关注。这个项目涉及探索次级配位球的一个具体方面：有机金属络合物中配体结构特征的互连(即，拓扑)。将合成并研究镍配合物，以确定配体的拓扑结构是否影响C-H活化。更具体地说，将研究配体二级结构中半活性施主对镍络合物C-H活化率的影响。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

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.