CAS: Accessing and Tuning the Reactivity of Late-Metal Oxo and Nitrido Complexes Using Iminoxolene Supporting Ligands

CAS：使用亚胺氧烯支持配体获取和调节后金属氧代和氮化配合物的反应性

• 批准号: 1955933
• 负责人: Seth Brown
• 金额: $ 49万
• 依托单位: University of Notre Dame
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-09-01 至 2023-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1955933&HistoricalAwards=false
• 关键词: CAS; Accessing; Tuning; Reactivity; Late

With support from the Chemical Catalysis (CAT) Program in NSF's Division of Chemistry, Professor Seth Brown of the University of Notre Dame is designing new kinds of catalysts to speed up important chemical reactions. The particular catalysts of interest promise to contribute to the US economy by enhancing the efficiency of chemical manufacturing. The project is focusing on metal-containing catalysts with attention to both the identity of the metal and the metal environment. Knowledge of the metal-environment interactions will guide the design of improved catalysts that will react with oxygen gas to produce commodity chemicals. This grant also supports the professional training of the graduate, undergraduate, and high school students who are conducting research under the supervision of Professor Brown. Educational materials suitable for high school or beginning college students are being developed in order to enhance scientific education on a larger scale. With support from the Chemical Catalysis (CAT) Program in NSF's Division of Chemistry, Professor Seth Brown of the University of Notre Dame is developing new oxidation catalysts. Oxidation reactions mediated by catalysts of the late transition metals are important in nature as well as in the chemical industry. Terminal oxo compounds are often invoked as reactive intermediates, but few well-characterized examples are known. Specifically, Professor Brown is exploring the ability of ancillary ligands that strongly perturb the electronic structure of the metals to allow access to, or modify the properties of, terminal oxo and nitrido groups bonded to late transition metals. Synthetic, spectroscopic, and computational studies are carried out on such complexes to clarify the nature of the metal-ligand interactions and how these interactions modify the properties of the metal-oxo linkage. These studies are complemented by detailed mechanistic studies of reactions such as alkane hydroxylation or dehydrogenation to elucidate design rules. These insights contribute to the design and implementation of new oxidation catalysts with enhanced reactivity or selectivity. This project supports the professional development of the graduate, undergraduate, and high school students in Professor Brown's research group, affording them the technical and intellectual skills that help them become successful in the scientific workforce. Educational materials centering on chemical kinetics, which underpins the study of catalysis, at an advanced high school/introductory college level are being developed and made broadly available.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NSF化学部的化学催化计划（CAT）计划的支持下，巴黎圣母院的塞思·布朗教授正在设计新型的催化剂，以加快重要的化学反应。 感兴趣的特定催化剂有望通过提高化学制造的效率来为美国经济做出贡献。 该项目着重于含金属的催化剂，并注意金属和金属环境的身份。 金属环境相互作用的知识将指导改进的催化剂的设计，这些催化剂将与氧气反应以产生商品化学物质。该赠款还支持在布朗教授的监督下进行研究的毕业生，本科生和高中生的专业培训。 为了大规模增强科学教育，正在开发适合高中或初学者的教育材料。在NSF化学部的化学催化（CAT）计划的支持下，巴黎圣母院的塞思·布朗教授正在开发新的氧化催化剂。晚期过渡金属催化剂介导的氧化反应在自然界和化学工业中都很重要。 末端的Oxo化合物通常被称为反应性中间体，但很少有特色的例子。具体而言，布朗教授正在探索辅助配体的能力，这些配体强烈扰乱了金属的电子结构，以允许键入或修改与后期过渡金属键合的末端Oxo和硝酸基团的性质。在此类复合物上进行了合成，光谱和计算研究，以阐明金属配体相互作用的性质，以及这些相互作用如何改变金属氧链接的性质。 这些研究通过详细的机械研究来补充，例如烷烃羟基化或脱氢作用，以阐明设计规则。 这些见解有助于具有增强的反应性或选择性的新氧化催化剂的设计和实施。 该项目支持布朗教授研究小组的毕业生，本科生和高中生的专业发展，为他们提供了帮助他们在科学劳动力中取得成功的技术和知识技能。 在高级高中/入门大学的研究中，正在开发并广泛提供有关催化研究的化学动力学的教育材料。该奖项反映了NSF的法定任务，并被认为是值得通过基金会的知识分子优点和更广泛影响的审查标准通过评估来通过评估来获得支持的。

项目成果

Optically active bis(aminophenols) and their metal complexes

光学活性双(氨基酚)及其金属配合物

• DOI: 10.1039/d3dt02436a
• 发表时间: 2023
• 期刊: Dalton Transactions
• 影响因子: 4
• 作者: Carbonel, Halen;Mikulski, Timothy D.;Nugraha, Kahargyan;Johnston, James;Wang, Yichun;Brown, Seth N.
• 通讯作者: Brown, Seth N.

Slip to π Ru: structural distortions due to metal-iminoxolene π bonding

滑向 Ï Ru：金属-亚氨基氧戊二烯 Ï 键合导致结构扭曲

• DOI: 10.1039/d3cc02943c
• 发表时间: 2023
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Ayson, Patricia Rose;Brown, Seth N.
• 通讯作者: Brown, Seth N.

Modulation of Isomerization and Ligand Exchange Rates by π Bonding in Bis(iminoxolene)iridium Pyridine Complexes

双(亚胺氧杂环戊烯)铱吡啶配合物中α键对异构化和配体汇率的调节

• DOI: 10.1021/acs.inorgchem.3c01717
• 发表时间: 2023
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Do, Thomas H.;Haungs, David A.;Chin, William Y.;Jerit, Jack T.;VanderZwaag, Analena;Brown, Seth N.
• 通讯作者: Brown, Seth N.

Mono- and Bis(iminoxolene)iridium Complexes: Synthesis and Covalency in π Bonding

单和双(亚胺氧杂环戊烯)铱配合物：α键的合成和共价键

• DOI: 10.1021/acs.inorgchem.1c04005
• 发表时间: 2022
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Do, Thomas H.;Brown, Seth N.
• 通讯作者: Brown, Seth N.