Synthetic, Mechanistic, and Catalytic Studies of Electrophilic d- and f-Element Complexes

亲电 d 元素和 f 元素配合物的合成、机理和催化研究

• 批准号: 1856619
• 负责人: Tobin Marks
• 金额: $ 61.5万
• 依托单位: Northwestern University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-08-01 至 2023-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1856619&HistoricalAwards=false
• 关键词: Synthetic; Mechanistic; Catalytic; Studies; Electrophilic

With this award, the Chemical Catalysis Program of the NSF Division of Chemistry is supporting the research of Professor Tobin J. Marks of Northwestern University in Evanston, Illinois. Professor Marks and his coworkers are discovering, understanding, and optimizing new catalytic reactions, and closely combining this effort with educational outreach activities. Such catalytic processes are of great importance to the U.S. chemical industry, and it is estimated that catalysis underpins 25% of the U.S. GDP, producing fertilizers, fuels, plastics, pharmaceuticals, coatings, and other chemicals on a huge scale. Future catalytic transformations must be more efficient, non-toxic, non-polluting, and use low-cost, earth-abundant metals in more selective, sustainable, and economically competitive technologies. Addressing these challenges will require a skilled National technical workforce, and US universities are playing a major role by broadly educating young scientists to attack global-scale problems, while conducting excellent research across broad disciplinary fronts. Projects funded by this award involve a multi-faceted, educationally rigorous mix of catalyst creation, catalytic reactions, and understanding reaction products. This, combined with a highly interactive research group environment, provides excellent training/mentoring for graduate, undergraduate, and postdoctoral scholars planning industrial, national laboratory, or academic careers, and includes women and underrepresented minorities. This research is built around two integrated exploratory, hypothesis-driven themes stimulated by the unique properties of earth-abundant lanthanide (4f), actinide (5f), and d0 early transition metal complexes. In the first, catalytic reactions that create or cleave carbon-heteroelement bonds via non-traditional pathways are being developed. Unusual catalysts are being used to selectively create heteroatom (boron, nitrogen, oxygen, sulfur, phosphorus) bonds to important chemical building blocks such as olefins, alkynes, ketones, aldehydes, esters and amides, either in single or in closely coupled multiple steps. Useful substances with diverse ring structures such as pharmaceuticals and fine chemicals and being produced by this work. Topics being studied include chiral ligands for pharma-related enantioselective catalytic processes, and catalytic systems capable of reversing the aforementioned bond-forming processes to deconstruct bio-based feedstocks and other heteroatom-containing molecules. In the second theme, catalyst nuclearity effects applied to unusual olefin polymerization and hydroelementation processes are being studied. The team is using designed catalytic centers to effect polymerization reactions which link unsaturated building blocks, including those with normally deactivating polar and basic groups, to produce plastic materials with superior bulk properties including mechanical or processing properties, and/or surface properties such as adhesion, wettability, water-repellence, compatibility with other polymers, or bacteriocidal characteristics. Catalyst design includes ways to orchestrate cooperative enzyme-like processes that are "switched on" when two catalytic centers are placed in close but variable proximity with the objective of achieving unique polymerization processes. These include polymerization reactions to produce novel types of polymer architectures derived from catalysts in which two cooperating metal centers have similar or different, complementary reactivities. A second goal with such catalysts is bond-forming processes which create expanded structures accessible only by the cooperative interaction of two catalytic metal centers.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.

凭借该奖项，美国国家科学基金会化学部的化学催化项目正在支持伊利诺伊州埃文斯顿西北大学托宾·J·马克斯教授的研究。马克斯教授和他的同事正在发现、理解和优化新的催化反应，并将这一努力与教育推广活动紧密结合起来。这种催化过程对美国化学工业非常重要，据估计催化支撑着美国 GDP 的 25%，大规模生产化肥、燃料、塑料、药品、涂料和其他化学品。未来的催化转化必须更加高效、无毒、无污染，并在更具选择性、可持续和经济竞争力的技术中使用低成本、地球储量丰富的金属。应对这些挑战需要一支熟练的国家技术队伍，而美国大学正在发挥重要作用，广泛教育年轻科学家解决全球范围的问题，同时在广泛的学科前沿开展出色的研究。该奖项资助的项目涉及催化剂创造、催化反应和理解反应产物等多方面、严格的教育组合。这与高度互动的研究小组环境相结合，为规划工业、国家实验室或学术职业的研究生、本科生和博士后学者提供了出色的培训/指导，其中包括女性和代表性不足的少数族裔。这项研究围绕两个综合探索性、假设驱动的主题展开，这些主题受到地球上丰富的镧系元素 (4f)、锕系元素 (5f) 和 d0 早期过渡金属配合物的独特性质的激发。首先，正在开发通过非传统途径创建或裂解碳-异质元素键的催化反应。不寻常的催化剂被用来选择性地在单个步骤或紧密耦合的多个步骤中与重要的化学结构单元（例如烯烃、炔烃、酮、醛、酯和酰胺）形成杂原子（硼、氮、氧、硫、磷）键。通过这项工作生产出具有多种环结构的有用物质，例如药品和精细化学品。正在研究的主题包括用于药物相关对映选择性催化过程的手性配体，以及能够逆转上述成键过程以解构生物基原料和其他含杂原子分子的催化系统。在第二个主题中，正在研究应用于不寻常的烯烃聚合和加氢元素化过程的催化剂核效应。该团队正在使用设计的催化中心来实现聚合反应，这些反应连接不饱和结构单元，包括那些通常失活的极性和碱性基团，以生产具有优异本体性能的塑料材料，包括机械或加工性能，和/或表面性能，如粘附性、润湿性、防水性、与其他聚合物的相容性或杀菌特性。催化剂设计包括协调类似酶的过程的方法，当两个催化中心紧密但可变地接近时，这些过程就会“启动”，以实现独特的聚合过程。这些包括聚合反应，以产生源自催化剂的新型聚合物结构，其中两个协同金属中心具有相似或不同的互补反应性。此类催化剂的第二个目标是成键过程，该过程只能通过两个催化金属中心的合作相互作用才能形成扩展的结构。该奖项反映了 NSF 的法定使命，并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，被认为值得支持。

项目成果

Homoleptic Lanthanide Amide Catalysts for Organic Synthesis: Experiment and Theory

• DOI: 10.1021/acscatal.0c04882
• 发表时间: 2021-02-12
• 期刊: ACS CATALYSIS
• 影响因子: 12.9
• 作者: Dicken, Rachel D.;Motta, Alessandro;Marks, Tobin J.
• 通讯作者: Marks, Tobin J.

Bis-Ferrocenyl-Pyridinediimine Trinuclear Mixed-Valent Complexes with Metal-Binding Dependent Electronic Coupling: Synthesis, Structures, and Redox-Spectroscopic Characterization

• DOI: 10.1021/jacs.0c10015
• 发表时间: 2020-10-28
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Carter, Cole;Kratish, Yosi;Marks, Tobin J.
• 通讯作者: Marks, Tobin J.

Selective Lanthanide‐Organic Catalyzed Depolymerization of Nylon‐6 to ϵ‐Caprolactam

选择性镧系元素—有机催化尼龙—6解聚为己内酰胺

• DOI: 10.1002/ange.202212543
• 发表时间: 2022
• 期刊: Angewandte Chemie
• 作者: Wursthorn, Lukas;Beckett, Kristen;Rothbaum, Jacob O.;Cywar, Robin M.;Lincoln, Clarissa;Kratish, Yosi;Marks, Tobin J.
• 通讯作者: Marks, Tobin J.

Alkane-Soluble Bis[tris(alkylphenyl)carbenium] Diborate Cocatalyst for Olefin Polymerizations

• DOI: 10.1021/acscatal.2c01676
• 发表时间: 2022-06-13
• 期刊: ACS CATALYSIS
• 影响因子: 12.9
• 作者: Gao, Yanshan;Christianson, Matthew D.;Marks, Tobin J.
• 通讯作者: Marks, Tobin J.

Versatile catalytic strategy for polar-functionalized, cross-linkable, self-healing, and photo-responsive polyolefins

用于极性功能化、可交联、自修复和光响应聚烯烃的多功能催化策略

• DOI: 10.1016/j.scib.2020.01.010
• 发表时间: 2020
• 期刊: Science Bulletin
• 影响因子: 18.9
• 作者: Gao, Yanshan;Marks, Tobin J.
• 通讯作者: Marks, Tobin J.