权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

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

职业：利用金属有机框架利用分子催化剂进行选择性 C-H 官能化

基本信息

批准号：
2044904
负责人：
Casey Wade
金额：
$ 68.5万
依托单位：
Ohio State University
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
2021
资助国家：
美国
起止时间：
2021-02-01 至 2026-01-31
项目状态：
未结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=2044904&HistoricalAwards=false
关键词：
CAREER Using Metal Organic Frameworks

项目摘要

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.

在化学系化学催化项目的资助下，俄亥俄州州立大学的Wade教授将通过研究含有能够选择性活化C-H键的固定化过渡金属络合物的新型非均相催化剂的设计来解决C-H键官能化的挑战。催化C-H键官能化提供了一种强大而有效的方法来制备用于制药和精细化工行业的复杂有机分子。然而，目前用于C-H官能化反应的许多催化剂依赖于稀有和昂贵的金属，并且需要高负载量以实现期望的活性水平。此外，对于能够促进含有多个C-H键的底物分子中的位点特异性官能化的催化剂存在日益增长的需求。这项研究将进一步了解催化剂固定化对催化活性和产物选择性的影响，并有可能影响精细化学品的生产。韦德博士将把他的研究与推广活动相结合，促进学生参与科学，技术，工程和数学（STEM）学科。韦德博士和他的团队将参与虚拟会见科学家，并将研究参与的机会带到化学教室（BORICC）计划，该计划将研究人员与缺乏STEM外展机会的地区的高中科学教室联系起来。这些计划旨在改善学生对科学家的看法，提高追求STEM职业的热情，并支持STEM领域的中学教育目标和课程。催化剂失活过程，如二聚和配体反离子化是普遍的均相反应。金属有机骨架（MOFs）为设计单中心多相催化剂提供了多功能平台，所述单中心多相催化剂由于位置隔离效应而抵抗分子间失活和分解过程。MOFs的良好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次级配位层，并实现区域或化学选择性转化。在化学部化学催化计划的资助下，Wade博士将研究设计基于MOF的C-H硼化和胺化催化剂的新策略，这些催化剂含有骨架固定的有机金属活性位点。这些研究利用接头和金属节点的明确空间排列来产生非共价相互作用，所述非共价相互作用陪伴分子底物进行位点选择性C-H键活化。将采用基准研究来评估不同催化剂固定化策略和MOF载体对催化活性和选择性的影响。该奖项反映了NSF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。