CAREER: Using Metal-Organic Frameworks to Harness Molecular Catalysts for Selective C-H Functionalization

在化学系化学催化项目的资助下，俄亥俄州立大学的Wade教授将通过研究含有能够选择性激活C-H键的固定化过渡金属配合物的新型非均相催化剂的设计，来解决C-H键功能化的挑战。催化C-H键功能化提供了一种强大而有效的方法来制备复杂的有机分子，用于制药和精细化工工业。然而，目前用于碳氢官能化反应的许多催化剂依赖于稀有和昂贵的金属，并且需要高负荷才能达到理想的活性水平。此外，对于能够促进含有多个C-H键的底物分子中特定位点功能化的催化剂的需求也在不断增长。本研究将加深对催化剂固定化对催化活性和产物选择性的影响的理解，并有可能影响精细化学品的生产。Wade博士将把他的研究与推广活动结合起来，促进学生参与科学、技术、工程和数学（STEM）学科。Wade博士和他的团队将参与“与科学家虚拟会面”和“为化学教室带来参与研究的机会”（BORICC）项目，该项目将研究人员与缺乏STEM外展机会的地区的高中科学教室联系起来。这些项目旨在提高学生对科学家的看法，增加追求STEM职业的热情，并支持STEM领域的中等教育目标和课程。催化剂失活过程，如二聚化和配体歧化是普遍的均相反应。金属有机框架（MOFs）为设计单位点非均相催化剂提供了通用平台，这些催化剂由于位点隔离效应而能够抵抗分子间失活和分解过程。mof的有序结构也提供了前所未有的机会来操纵催化位点周围的二级配位球，并实现区域或化学选择性转化。在化学部化学催化项目的资助下，Wade博士将研究设计基于mof的含框架固定化有机金属活性位点的C-H硼化和胺化催化剂的新策略。这些研究利用连接体和金属节点的明确的空间排列来产生非共价相互作用，这些相互作用伴随着底物进行选择性的C-H键激活。基准研究将用于评估不同的催化剂固定策略和MOF载体对催化活性和选择性的影响。结构-性能关系将发展和应用于设计优化的选择性C-H硼化和胺化催化剂。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 funding from the Chemical Catalysis program in the Division of Chemistry, Professor Wade of The Ohio State University will address the challenges in C–H bond functionalization by investigating the design of new heterogeneous catalysts containing immobilized transition metal complexes capable of selective C–H bond activation. Catalytic C–H bond functionalization offers a powerful and efficient means of preparing complex organic molecules used in the pharmaceutical and fine chemical industries. However, many catalysts currently employed for C–H functionalization reactions rely on rare and expensive metals and require high loadings to achieve a desirable level of activity. In addition, there is a growing need for catalysts capable of facilitating site-specific functionalization in substrate molecules containing multiple C–H bonds. This research will develop greater understanding of the effects of catalyst immobilization on catalytic activity and product selectivity, and has the potential to impact the production of fine chemicals. Dr. Wade will integrate his research with outreach activities that promote student engagement in science, technology, engineering and mathematics (STEM) disciplines. Dr Wade and his team will be involved in Virtual Meet a Scientist and Bringing Opportunities for Research Involvement to Chemistry Classrooms (BORICC) programs that connect researchers with high school science classrooms in regions that lack access to STEM outreach opportunities. These programs are designed improve student perceptions of scientists, increase enthusiasm for pursuing STEM-based careers, and support secondary education goals and curricula in STEM fields. Catalyst deactivation processes such as dimerization and ligand disproportionation are prevalent in homogeneous reactions. Metal-organic frameworks (MOFs) offer versatile platforms for the design of single-site heterogeneous catalysts that are resistant to intermolecular deactivation and decomposition processes owing to site-isolation effects. The well-ordered structures of MOFs also offer unprecedented opportunities to manipulate the secondary coordination sphere around a catalytic site and enable regio- or chemo-selective transformations. With funding from the Chemical Catalysis Program of the Chemistry Division, Dr. Wade will investigate new strategies for the design MOF-based C–H borylation and amination catalysts containing framework-immobilized, organometallic active sites. These studies exploit the well-defined spatial arrangement of linkers and metal nodes to engender non-covalent interactions that chaperone substrates for site-selective C–H bond activation. Benchmarking studies will be employed to evaluate the effect of different catalyst immobilization strategies and MOF supports on catalytic activity and selectivity. Structure-property relationships will be developed and applied for design optimization of site-selective C–H borylation and amination catalysts.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.