Metal-Ligand and Metal-Metal Cooperativities as Design Principles for Base Metal Catalysis

金属-配体和金属-金属协同作用作为贱金属催化的设计原则

• 批准号: 1800151
• 负责人: Hairong Guan
• 金额: $ 45万
• 依托单位: University of Cincinnati Main Campus
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-09-01 至 2021-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800151&HistoricalAwards=false
• 关键词: Metal; Ligand; Cooperativities; Design; Principles

With funding from the Chemical Catalysis Program of the Chemistry Division, Dr. Hairong Guan of the University of Cincinnati is developing new catalysts for the synthesis of organic molecules. Catalysis reactions play indispensable roles in making new drugs and novel materials, reducing energy consumption, preventing chemical waste, and utilizing renewable feedstocks. Precious metals such as ruthenium, rhodium, palladium, iridium, and platinum are often used in catalytic reactions. However, they are expensive, limited in supply, and difficult to remove from the chemical products. To develop more sustainable syntheses, efforts are being directed at using base metals, which include iron, cobalt, nickel and copper, for catalysis. The difficulty is that catalysts derived from these metals are usually less reactive and more prone to decomposition. In this project, Dr. Guan is developing new catalysts featuring cooperativity between a metal and a ligand, or cooperativity between two metals. With this strategy, catalysts derived from inexpensive and abundant metals are more efficient and robust, mimicking the reactivity of their precious metal analogs. Dr. Guan develops research-based educational materials for an undergraduate laboratory course focusing on catalysis. He also provides research opportunities to students from groups that are underrepresented in the STEM fields, enhancing student professional development through his collaborations with the local chemical industry. This research enhances national welfare, by providing sustainable innovation in advanced chemical manufacturing, renewable energy and chemical industry. Dr. Guan is developing new strategies to design base metal catalysts with reactivity akin to the precious metal catalysts. Iron and copper complexes supported by tridentate ligands capable of transferring protons are synthesized and tested for catalytic hydrogenation of aldehydes, ketones, esters, amides, and carbon dioxide (CO2). Heterobimetallic complexes of Fe-Cu or Fe-Zn are prepared and used to catalyze reduction reactions under water-gas shift reaction conditions. These reactions may be relevant to industry, for example manufacturing of detergent alcohols. The catalysts may also have impact in the areas of carbon dioxide conversion and energy storage. Mechanistic studies are carried out for a better understanding of structure-reactivity relationships, particularly the synergy between ligand and metal or between two metals. In support of the broader impacts of the project, Dr. Guan is actively engaged in programs focusing on providing research opportunities to underrepresented STEM students including those at collaborating primarily undergraduate institutions and community colleges. Through research-based teaching and collaborations with local companies, Dr. Guan is assisting students to develop their creative and critical thinking skills and facilitating their career 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.

辛辛那提大学的关海荣博士在化学系化学催化项目的资助下，正在开发用于有机分子合成的新催化剂。催化反应在制备新药和新材料、降低能耗、防止化学废物和利用可再生原料等方面发挥着不可或缺的作用。贵金属如钌、铑、钯、铱和铂常用于催化反应。然而，它们价格昂贵，供应有限，并且难以从化学产品中去除。为了开发更可持续的合成，正在努力使用贱金属，包括铁，钴，镍和铜，用于催化。困难在于，由这些金属衍生的催化剂通常反应性较低，更容易分解。在这个项目中，关博士正在开发具有金属和配体之间或两种金属之间的协同作用的新催化剂。通过这种策略，来自廉价和丰富的金属的催化剂更有效和耐用，模仿其贵金属类似物的反应性。关博士为本科实验室课程开发基于研究的教学材料，重点是催化。他还提供了研究机会，从在干领域代表性不足的群体的学生，通过他与当地化工行业的合作，提高学生的专业发展。 该研究通过在先进化学制造，可再生能源和化学工业中提供可持续创新来提高国家福利。Guan博士正在开发新的策略来设计具有与贵金属催化剂类似的反应性的贱金属催化剂。铁和铜配合物支持的三齿配体能够转移质子的合成和测试的醛，酮，酯，酰胺，和二氧化碳（CO2）的催化氢化。制备了Fe-Cu或Fe-Zn的杂多配合物，并用于在水煤气变换反应条件下催化还原反应。这些反应可能与工业有关，例如洗涤剂醇的制造。 这些催化剂还可能在二氧化碳转化和能量储存领域产生影响。机理的研究进行了更好地理解的结构-反应性的关系，特别是配体和金属之间或两种金属之间的协同作用。为了支持该项目的更广泛影响，关博士积极参与各种项目，重点是为代表性不足的STEM学生提供研究机会，包括那些主要合作的本科院校和社区学院。通过研究型教学和与当地公司的合作，关博士帮助学生培养创造性和批判性思维能力，促进他们的职业发展。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力审查标准进行评估，被认为值得支持。

项目成果

POCOP-type cobalt and nickel pincer complexes bearing an appended phosphinite group

带有附加次膦酸盐基团的 POCOP 型钴和镍钳形配合物

• DOI: 10.1139/cjc-2020-0137
• 发表时间: 2021
• 期刊: Canadian Journal of Chemistry
• 影响因子: 1.1
• 作者: Li, Yingze;Krause, Jeanette A.;Guan, Hairong
• 通讯作者: Guan, Hairong

Multiweek Experiments for an Inorganic Chemistry Laboratory Course: Synthesis of Nickel Complexes Supported by a Tetradentate Ligand with a N 2 O 2 Donor Set

无机化学实验室课程的多周实验：由具有 N 2 O 2 供体组的四齿配体支持的镍配合物的合成

• DOI: 10.1021/acs.jchemed.0c01117
• 发表时间: 2021
• 期刊: Journal of Chemical Education
• 影响因子: 3
• 作者: Collett, Joel D.;Krause, Jeanette A.;Guan, Hairong
• 通讯作者: Guan, Hairong

Hydrogenation Reactions Catalyzed by PNP-Type Complexes Featuring a HN(CH2CH2PR2)2 Ligand

• DOI: 10.1007/3418_2020_63
• 发表时间: 2020
• 作者: Dewmi Ekanayake;Hairong Guan

Dehydrogenative Coupling of Aldehydes with Alcohols Catalyzed by a Nickel Hydride Complex

• DOI: 10.1021/acs.organomet.8b00888
• 发表时间: 2019-04-08
• 期刊: ORGANOMETALLICS
• 影响因子: 2.8
• 作者: Eberhardt, Nathan A.;Wellala, Nadeesha P. N.;Guan, Hairong
• 通讯作者: Guan, Hairong

An Iron‐Hydrogen Bond Resistant to Protonation and Oxidation

抗质子化和氧化的铁氢键

• DOI: 10.1002/zaac.202100066
• 发表时间: 2021
• 期刊: Zeitschrift für anorganische und allgemeine Chemie
• 作者: Collett, Joel D.;Ransohoff, Rebecca W.;Krause, Jeanette A.;Guan, Hairong
• 通讯作者: Guan, Hairong