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.

在化学催化计划中，辛辛那提大学的Hairong Guan教授将使用金属 - 氢键（即金属氢化物）作为催化剂来研究分子，作为催化剂，用于促进或还原脂肪酸甲基酯，二氧化物二氧化物和糖源性多醇。对于制造商表面活性剂在许多消费产品中使用的化学工业非常需要这些催化过程，并将可再生材料转换为燃料和增值化学品。该项目将重点介绍使用含有锰，铁，钴，镍和铜等地球丰富，廉价的金属来设计这种催化剂。为了增强金属氢化物的反应性并最大程度地减少催化剂的降解，不仅会参与氢转移，而且与金属紧密结合的配体将被雇用。该项目将通过许多计划，包括美国化学学会项目种子计划，本科生的NSF研究经验以及辛辛那提大学的科学与工程学女性（WISE）计划的许多计划。 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许多氢化或还原过程中的中间体。分叉性和强烈的螯合配体将在以下假设下设计，即他们可以认为金属扮演的角色，参与两电子转移或抑制群集的形成。具体的研究目标包括基于铁和镍的更健壮和活跃的氢化催化剂，锰和钴的羟基环戊二烯基络合物的设计，以及作为掩盖的金属氢化物的设计，以及追求磷酸化的单核铜氢化物。为了支持该项目的更广泛影响，关教授将积极参与专注于提供研究机会的计划，以提供代表性不足的少数族裔学生，包括合作的小学本科机构。基于研究的教材将在化学教育文献和其他机构中更广泛地传播。与本地公司的积极合作将旨在在工业环境中提高学生解决问题的技能。该奖项反映了NSF的法定任务，并通过使用基金会的知识分子优点和更广泛的影响审查标准来评估被认为是宝贵的支持。

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