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.

在化学催化计划的支持下，加利福尼亚大学的塞思·科恩（Seth Cohen）教授，圣地亚哥正在研究开发一类新的可调，可调的催化材料。 Cohen教授及其研究团队将使用与钯，菱形和金属金属中心相关的磷衍生的配体的结合，将创建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基化反应（一氧化碳捕获和掺入有用的构件中），这些反应对于制造精细化学品，药品和其他重要产品很重要。除了这些研究之外，科恩教授还支持来自加利福尼亚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）在公共政策和科学的界面参加实习，并同时创造了本科生的科学政策课程，以使其对新的化学效果进行新的化学效果，并以新的化学作品来促进新的化学效果，并以新的化学作品来促进新的化学效果。该研究计划正在开发一类新的固态催化剂，用于进行高价值化学转化。具体而言，正在研究源自基于磷的配体框架和低氧化态反应金属的金属有机框架（MOF，一种多孔固体）。低氧化态金属作为MOF的组成部分并不常见，并且不发达，但对于C-C键形成反应而言可能有价值。 MOF催化剂的有机成分和金属成分都将以模块化的方式进行检查，以研究结构功能关系，优化催化活性并探索选择性的机会。 这些研究旨在确定氧化状态低，框架材料可以用作模块化的下一代固态催化剂。从协同上讲，这些活动将促进对多样化的研究生和本科生的培训，同时还支持科学政策实习计划的本科生参与，并通过课程发展扩大科学政策讨论。这项奖项反映了NSF的法定任务，并通过该基金会的知识分子优点和广泛的影响来评估NSF的法定任务。

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.