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化学系化学催化(CAT)项目的支持下，圣母大学的Seth Brown教授正在设计新型催化剂，以加速重要的化学反应。特殊的利益催化剂有望通过提高化学制造的效率为美国经济做出贡献。该项目将重点放在含有金属的催化剂上，同时注意金属的特性和金属环境。金属-环境相互作用的知识将指导改进的催化剂的设计，这种催化剂将与氧气反应生成商品化学品。这笔助学金还支持在布朗教授的指导下进行研究的研究生、本科生和高中生的专业培训。为了在更大范围内加强科学教育，正在开发适合高中生或大学初学者的教材。在NSF化学系化学催化(CAT)项目的支持下，圣母大学的Seth Brown教授正在开发新的氧化催化剂。后过渡金属催化剂催化的氧化反应在自然界和化学工业中都具有重要意义。末端氧化合物经常作为活性中间体被引用，但鲜有已知的良好表征的例子。具体地说，布朗教授正在探索辅助配体的能力，这些配体强烈扰乱金属的电子结构，使其能够访问或改变连接到后过渡金属上的末端氧基和硝基的性质。对这类配合物进行了合成、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-氧键的性质。这些研究还包括对烷烃羟化或脱氢等反应的详细机理研究，以阐明设计规则。这些见解有助于设计和实施具有更高反应活性或选择性的新型氧化催化剂。该项目支持布朗教授研究小组中的研究生、本科生和高中生的专业发展，为他们提供技术和智力技能，帮助他们在科学工作中取得成功。以化学动力学为基础的高级高中/大学入门课程的教材正在开发中，并广泛提供。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

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.