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

在NSF化学部化学催化（CAT）计划的支持下，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。 感兴趣的特定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。 该项目的重点是含金属催化剂，同时关注金属的特性和金属环境。 金属与环境相互作用的知识将指导改进催化剂的设计，这些催化剂将与氧气反应以生产商品化学品。该补助金还支持研究生，本科生和高中生的专业培训，他们在布朗教授的监督下进行研究。 正在编制适合高中生或大学新生的教育材料，以便在更大范围内加强科学教育。在NSF化学部化学催化（CAT）计划的支持下，圣母大学的Seth Brown教授正在开发新的氧化催化剂。由后过渡金属催化剂介导的氧化反应在自然界以及化学工业中是重要的。 末端氧代化合物经常被用作活性中间体，但很少有充分表征的例子是已知的。具体来说，布朗教授正在探索辅助配体的能力，这些配体强烈干扰金属的电子结构，以允许进入或修改与后过渡金属键合的末端氧代和氮基的性质。合成，光谱和计算研究进行了这样的配合物，以澄清金属配体相互作用的性质，以及这些相互作用如何修改的金属-氧代键的性质。 这些研究的补充，如烷烃羟基化或脱氢反应的详细机理研究，阐明设计规则。 这些见解有助于设计和实施具有增强的反应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，帮助他们在科学劳动力中取得成功。 该奖项反映了NSF的法定使命，通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

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.