CAREER: CAS: Understanding the Chemistry of Palladium and Silyl Compounds to Design Catalyst Active Sites

在这个由化学部化学结构、动力学机制B计划资助的CAREER项目中，俄勒冈州大学化学和生物化学系的阿曼达·库克-斯内森正在通过理解分子在液-固界面上的相互作用来开发新的催化剂。 该研究计划的最终目标是开发具有活性位点的固体催化剂-催化剂上化学反应的位置-在结构上被理解。固体催化剂在化学工业中广泛使用，但了解它们的功能具有很大的挑战性。只有在分子水平上了解活性中心的结构，才能提出关于如何改进反应的假设。 在本项目中，将在二氧化硅（沙子和玻璃的主要成分）表面安装由钯制成的活性位点，以合成固体催化剂，并对其活性和作用机理进行研究。该研究计划位于有机和无机化学以及均相和多相催化的界面，有可能为更可持续的未来做出贡献。由于研究的跨学科性质，从事该项目的学生将在智力和实践方面受益。导师制，高中学生沉浸在化学实验室，并通过推广增加多样性，公平性和包容性也是该项目的一部分。多相催化在化学工业中至关重要，它用于90%的化学过程。这些催化剂是可持续实践的组成部分，因为它们是强大的和可回收的。非均相催化剂的改进通常是经验性的，并且由于缺乏对活性位点的结构理解而受到阻碍，从而排除了信息性的机理研究。该项目利用表面有机金属化学来控制表面上金属位点的结构和反应性，特别是二氧化硅上负载的钯位点。有三个目标：1）将形成表面负载的（甲硅烷基）Pd（H）物种，并将测试它们作为烯烃异构化催化剂的反应活性; 2）将研究甲硅烷基卤化物对钯络合物的氧化加成; 3）将合成阳离子表面负载的钯位点，并将证明它们在Diels-Alder反应中的催化活性。 除了研究目标，还有几个补充教育目标：1）通过有效的指导进行教育，2）增加STEM的代表性，3）提高对来自代表性不足和边缘化群体的化学家贡献的认识。该奖项反映了NSF的法定使命，并被认为值得通过使用基金会的智力价值和更广泛的影响审查标准进行评估来支持。

In this CAREER project, funded by the Chemical Structure, Dynamics & Mechanisms B Program of the Chemistry Division, Amanda Cook-Sneathen of the Department of Chemistry and Biochemistry at the University of Oregon is developing new catalysts by understanding the interactions of molecules at a liquid-solid interface. The ultimate goal of this research program is to develop solid catalysts that have an active site – the location of chemical reactions on a catalyst – that is structurally understood. Solid catalysts are used ubiquitously in the chemical industry but understanding how they function is significantly challenging. Only with knowledge of the active site structure on a molecular level can one develop hypotheses on how to improve reactions. In this project, active sites made of palladium will be installed on the surface of silica (the primary component of sand and glass) to synthesize solid catalysts, and their activities and mechanisms of action will be investigated. This research program sits at the interface of organic and inorganic chemistry and homogeneous and heterogeneous catalysis and has the potential to contribute to a more sustainable future. Students working on this project will benefit intellectually and practically because of the interdisciplinary nature of the research. Mentorship, immersion of high-school students in chemistry labs, and increasing diversity, equity, and inclusion through outreach are also parts of the project. Heterogeneous catalysis is vital in the chemical industry, where it is used in 90% of chemical processes. These catalysts are integral to sustainable practices, since they are robust and recyclable. Improvement of heterogeneous catalysts is often empirical and is hindered by a lack of structural understanding of the active site, precluding informative mechanistic studies. This project utilizes surface organometallic chemistry to control the structure and reactivity of metal sites on surfaces, specifically palladium sites supported on silica. There are three Aims: 1) Surface-supported (silyl)Pd(H) species will be formed and their reactivity as catalysts for alkene isomerization will be tested; 2) Oxidative addition of silyl halides to palladium complexes will be investigated; 3) Cationic, surface-supported palladium sites will be synthesized, and their catalytic activity in the Diels-Alder reaction will be demonstrated. In addition to the research goals, there are several complementary educational goals: 1) educate through effective mentorship, 2) increase representation in STEM, and 3) increase awareness of contributions of chemists from underrepresented and marginalized groups.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.