CAREER: Poly(hydrosilyl) rare earth compounds for new organosilane transformations and catalysis

在化学系化学催化计划的支持下，爱荷华州立大学化学系的Aaron Sadow教授将通过详细的核磁共振、红外光谱和X射线衍射研究，深入了解聚(氢硅基)稀土化合物的独特结构和电子性质，并进一步探索可能的Ln-SiH相互作用和电子离域。萨杜教授的这一提议旨在更好地理解镧系元素-硅键的反应性。F元素硅基化合物的化学还处于起步阶段，因此开发其潜力具有重要意义。通过使用具有Si-H基团的配体将进一步加强拟议的研究，这些配体可以参与并为生成的稀土硅基提供有趣的反应途径。该提议寻求合成Ln-Si络合物的各种途径。将在本项目过程中开发的新的聚(氢硅基)阴离子可能会在本提案范围之外的硅、主基或有机金属化学的其他领域中得到应用。在化学系化学催化计划的支持下，Sadow教授将探索一个已知相对较少的稀土硅基化合物，甚至更少的含有SiH基团的化学领域。稀土金属-硅([Ln]-SiR3)化合物的大部分化学成分都是未知的。发现了聚(氢硅基)稀土化合物最有利的反应途径，特别是涉及配体上SiH基团的消除和提取反应，并对其反应机理进行了探讨。澄清这些结构、成键和反应性问题将促进新的催化化学。更广泛的影响和教育计划建立在增加爱荷华州本科生专业数量的坚实理由基础上，并结合值得赞扬的外联活动。PI建议为本科生开发一门课程，以探索职业问题并激发学生对化学的兴趣。私家侦探有一位化学教育同事伯内特博士在船上。对于参与这一研究项目的研究生来说，与奥地利格拉茨大学Marschner教授团队的合作将提供国际科学专业知识交流。

With the support of the Chemical Catalysis Program in the Chemistry Division, Professor Aaron Sadow of the Chemistry Department at Iowa State University will provide insight into the unique structural and electronic properties of poly(hydrosilyl)lanthanide compounds using detailed NMR and infrared spectroscopic and X-ray diffraction studies and to further explore possible Ln-SiH interactions and electronic delocalization. This proposal by Professor Sadow aims to better understand the reactivity of lanthanide-silicon bonds. The chemistry of f-element silyl complexes is still in its infancy, so exploration of its potential is of great importance. The proposed studies will be further enhanced by using ligands with Si-H groups which can participate and provide interesting reactivity pathways of the resulting lanthanide silyl. The proposal seeks various routes to the synthesis of Ln-Si complexes. The new poly(hydrosilyl) anions that will be developed during the course of this project may find application in other areas of silicon, main group or organometallic chemistry beyond the scope of this proposal. The reactivity of the resulting materials will also be studied and compared to their carbon analogs.With the support of the Chemical Catalysis Program in the Chemistry Division, Professor Sadow will explore an area of chemistry where relatively few rare earth silyl compounds are known and even fewer contain SiH groups. Much of the chemistry of rare earth metal-silicon ([Ln]-SiR3) compounds is unexplored. The most favorable reaction pathways of poly(hydrosilyl) rare earth compounds, particularly elimination and abstraction reactions involving the SiH moieties on the ligands, will be discovered and their mechanisms will be investigated. Clarification of these structural, bonding, and reactivity issues will facilitate new catalytic chemistry. Broader Impacts and the Educational Plan are built on a solid rationale to increase the number of undergraduate majors at Iowa State, combined with outreach activities, which are commendable. The PI proposes to develop a course for undergraduates to explore career issues and to generate interest in chemistry. The PI has a chemical education colleague, Dr. Burnett on board. For the graduate students engaged in this research project, collaboration with Professor Marschner's group at the University of Graz in Graz, Austria will provide an international exchange of scientific expertise.