Tunable Catalysts Based on Low Valent Metal-Phosphine Framework Materials

基于低价金属-膦骨架材料的可调催化剂

• 批准号: 2153240
• 负责人: Seth Cohen
• 金额: $ 52.5万
• 依托单位: University of California-San Diego
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-06-01 至 2025-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2153240&HistoricalAwards=false
• 关键词: Tunable; Catalysts; Based; Low; Valent

With the support of the Chemical Catalysis Program in the Division of Chemistry, Professor Seth Cohen of the University of California, San Diego is studying the development of a new class of solid, tunable catalytic materials. Using a combination of phosphorus-derived ligands linked to palladium, rhodium, and iridium metal centers, Professor Cohen and his research team will create new molecular frameworks with potential for catalysis. Modifications to these materials are being explored to determine how to tune them to promote cross-coupling and hydroformylation reactions (carbon monoxide capture and incorporation into useful building blocks) that are important for the manufacture of fine chemicals, pharmaceuticals, and other important products. In addition to these studies, Professor Cohen is supporting undergraduate students from across the University of California system to travel to Washington DC where they can participate in internships at the interface of public policy and science through the Science Policy Internship Program (SPIP), and is simultaneously creating an undergraduate scientific policy course.Innovative catalytic materials are essential to keep up with demand for new chemical reactions that produce fine chemicals, pharmaceuticals, and other important products. This research program is developing a new class of solid-state catalysts for performing high-value chemical transformations. Specifically, metal-organic frameworks (MOFs, a type of porous solid) derived from phosphorus-based ligand frameworks and low oxidation state reactive metals are being investigated. The use of low oxidation state metals as a component of MOFs is uncommon and underdeveloped, but potentially valuable for C-C bond forming reactions. Both the organic and metal component of the MOF catalysts will be examined in a modular manner, to investigate structure-function relationships, optimize catalytic activity, and explore opportunities for selectivity. These studies are designed to determine how low oxidation state, framework materials can serve as modular, next-generation, solid state catalysts. Synergistically, these activities will promote the training of a diverse group of graduate and undergraduate students, while also supporting science policy internship program participation for undergraduates and broadening scientific policy discussion through course development.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支持下，加州大学圣地亚哥分校的Seth Cohen教授正在研究一种新型固体可调催化材料的开发。科恩教授和他的研究团队将利用磷衍生配体与钯、铑和铱金属中心相连的组合，创造出具有催化潜力的新分子框架。正在探索对这些材料的修改，以确定如何调整它们以促进交叉偶联和氢甲酰化反应（一氧化碳捕获并纳入有用的构建块），这对精细化学品，药品和其他重要产品的制造很重要。除了这些研究之外，科恩教授还支持加州大学系统的本科生前往华盛顿特区，在那里他们可以通过科学政策实习计划（SPIP）参加公共政策和科学的实习，同时创建一个本科生科学政策课程。创新的催化材料对于满足生产精细化学品、药品和其他重要产品的新化学反应的需求至关重要。该研究项目正在开发一种新型固态催化剂，用于高价值的化学转化。具体来说，由磷基配体框架和低氧化态活性金属衍生的金属有机框架（MOFs，一种多孔固体）正在研究中。使用低氧化态金属作为mof的组成部分是不常见和不发达的，但在C-C键形成反应中具有潜在的价值。MOF催化剂的有机和金属成分将以模块化的方式进行研究，以研究结构-功能关系，优化催化活性，并探索选择性的机会。这些研究旨在确定低氧化态框架材料如何作为模块化的下一代固态催化剂。协同作用下，这些活动将促进培养多样化的研究生和本科生群体，同时也支持本科生参与科学政策实习项目，并通过课程开发扩大科学政策讨论。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。

项目成果

A Coordination Polymer of Vaska's Complex as a Heterogeneous Catalyst for the Reductive Formation of Enamines from Amides

Vaska络合物的配位聚合物作为酰胺还原生成烯胺的多相催化剂

• DOI: 10.1002/anie.202301611
• 发表时间: 2023
• 期刊: Angewandte Chemie International Edition
• 作者: Griffin, Samuel E.;Domecus, Grant P.;Flores, Clarissa E.;Sikma, R. Eric;Benz, Lauren;Cohen, Seth M.
• 通讯作者: Cohen, Seth M.

Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers

多位膦连接体合成低价金属有机骨架的实验方法

• DOI: 10.3791/65317
• 发表时间: 2023
• 期刊: Journal of Visualized Experiments
• 作者: Griffin, Samuel E.;Domecus, Grant P.;Cohen, Seth M.
• 通讯作者: Cohen, Seth M.