CAS: Taming the Reactivity of Base Metal Hydrides Through Bifunctional Ligands

CAS：通过双功能配体控制贱金属氢化物的反应性

• 批准号: 2102192
• 负责人: Hairong Guan
• 金额: $ 50万
• 依托单位: University of Cincinnati Main Campus
• 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: 2021-09-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2102192&HistoricalAwards=false
• 关键词: CAS; Taming; Reactivity; Base; Metal

With the support of the Chemical Catalysis program in the Division of Chemistry, Professor Hairong Guan of the University of Cincinnati will study molecules with metal-hydrogen bonds (i.e., metal hydrides) as catalysts for the hydrogenation or reduction of fatty acid methyl esters, carbon dioxide, and sugar-derived polyols. These catalytic processes are highly desirable to the chemical industry that manufactures surfactants used in many consumer products, and converts renewable materials to fuels and value-added chemicals. This project will focus on the use of earth-abundant, inexpensive metals such as manganese, iron, cobalt, nickel, and copper to design such catalysts. To enhance the reactivity of the metal hydrides and to minimize degradation of the catalysts, ligands that not only participate in hydrogen transfer but also bind tightly to the metals will be employed. The project will contribute to the rigorous training of a diverse group of high school, undergraduate, and graduate students via a number of programs including the American Chemical Society Project SEED Program, the NSF Research Experience for Undergraduates program, and the University of Cincinnati’s Women in Science and Engineering (WISE) Program. Through this project, Professor Guan will also develop research-based materials for a laboratory course that can be used by community colleges or institutions with limited resources, provide research opportunities to underrepresented minority students, and enhance student professional development through collaborations with local chemical companies.With the support of the Chemical Catalysis program in the Division of Chemistry, Professor Hairong Guan of the University of Cincinnati will study the strategies of improving the reactivity of base metal hydrides, which are key intermediates in many hydrogenation or reduction processes. Bifunctional and strongly chelating ligands will be designed under the hypothesis that they can deemphasize the roles played by the metals, participate in two-electron transfer, or suppress cluster formation. The specific research objectives include the development of more robust and active hydrogenation catalysts based on iron and nickel, the design of hydroxycyclopentadienyl complexes of manganese and cobalt as masked metal hydrides, and the pursuit of phosphine-ligated mononuclear copper hydrides. In support of the broader impacts of the project, Professor Guan will actively engage in programs focusing on providing research opportunities to underrepresented minority students including those from collaborating primarily undergraduate institutions. Research-based teaching materials will be disseminated more broadly in the chemical education literature and to other institutions. Active collaborations with local companies will be geared toward enhancing student problem-solving skills in an industrial setting.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，辛辛那提大学关海荣教授将研究具有金属氢键的分子（即金属氢化物）作为脂肪酸甲酯加氢或还原的催化剂，碳这些催化过程对于生产用于许多消费品的表面活性剂以及将可再生材料转化为燃料和增值化学品的化学工业来说是非常理想的。该项目将重点使用地球上丰富的廉价金属（例如锰、铁、钴、镍和铜）来设计此类催化剂，以增强金属氢化物的反应性并最大限度地减少催化剂和配体的降解。该项目将通过包括美国化学会项目 SEED 计划在内的多个项目，为高中生、本科生和研究生的多元化群体提供严格的培训。 ,通过该项目，管教授还将为实验室课程开发基于研究的材料，供社区学院或机构使用。辛辛那提大学关海荣教授将利用有限的资源，为代表性不足的少数族裔学生提供研究机会，并通过与当地化工公司的合作增强学生的专业发展。在化学系化学催化项目的支持下，辛辛那提大学的关海荣教授将研究改善贱金属氢化物是许多氢化或还原过程中的关键中间体，其反应活性将根据以下假设进行设计：它们可以弱化金属所起的作用，参与双电子转移或抑制簇。具体研究目标包括开发基于铁和镍的更坚固和活性更高的加氢催化剂，设计作为掩蔽金属的锰和钴的羟基环戊二烯基配合物。为了支持该项目的更广泛影响，关教授将积极参与旨在为代表性不足的少数族裔学生（包括来自主要以本科研究为基础的合作机构的学生）提供研究机会的项目。教材将在化学教育文献中更广泛地传播，并反映与当地公司的积极合作，旨在提高学生在工业环境中解决问题的技能。该奖项是 NSF 的法定使命和使命。通过使用基金会的智力优点和更广泛的影响审查标准进行评估，该项目被认为值得支持。

项目成果

The curious cases of tetrahydrosalen-type ligands interacting with Ni( ii ): structures and ligand-based oxidation reactions

四氢salen型配体与Ni(ii)相互作用的奇怪案例：结构和基于配体的氧化反应

• DOI: 10.1039/d3dt02023a
• 发表时间: 2023
• 期刊: Dalton Transactions
• 影响因子: 4
• 作者: Xu, Vivian;Pandey, Bedraj;Jayawardhena, J. P.;Krause, Jeanette A.;Guan, Hairong
• 通讯作者: Guan, Hairong

A Mechanistic Perspective on the Mechanochemical Method To Reduce Carbonyl Groups with Stainless Steel and Water

不锈钢和水机械化学法还原羰基的机理视角

• DOI: 10.1002/ejoc.202300149
• 发表时间: 2023
• 期刊: European Journal of Organic Chemistry
• 影响因子: 2.8
• 作者: Mokhtar, Mennatullah M.;Andersen, Joel M.;Kister, Ethan A.;Hopkins, Jordan X.;Estier, Tom;Hamilton, Fiona;Guan, Hairong;Mack, James;Haley, Rebecca A.
• 通讯作者: Haley, Rebecca A.

On the Demise of PPP-Ligated Iron Catalysts in the Formic Acid Dehydrogenation Reaction

• DOI: 10.1021/acs.inorgchem.3c03125
• 发表时间: 2023-10-31
• 期刊: INORGANIC CHEMISTRY
• 影响因子: 4.6
• 作者: Pandey，Bedraj;Krause，Jeanette A.;Guan，Hairong
• 通讯作者: Guan，Hairong