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

职业：用于新型有机硅烷转化和催化的聚（氢硅烷基）稀土化合物

• 批准号: 0955635
• 负责人: Aaron Sadow
• 金额: $ 60万
• 依托单位: Iowa State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2010
• 资助国家: 美国
• 起止时间: 2010-02-01 至 2015-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0955635&HistoricalAwards=false
• 关键词: CAREER; Poly; hydrosilyl; rare; earth

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.

在化学系化学催化项目的支持下，爱荷华州州立大学化学系的Aaron Sadow教授将利用详细的NMR、红外光谱和X射线衍射研究，深入了解聚（氢化硅烷基）镧系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。Sadow教授的这一提议旨在更好地理解镧系元素-硅键的反应性。氟元素硅基配合物的化学研究尚处于起步阶段，因此对其潜力的探索具有重要意义。通过使用具有Si-H基团的配体，可以进一步增强所提出的研究，所述配体可以参与并提供所得镧系硅烷基的有趣的反应途径。该提案寻求各种途径来合成Ln-Si络合物。在本项目过程中将开发的新的聚（氢化甲硅烷基）阴离子可能会在本提案范围之外的硅、主族或有机金属化学的其他领域中得到应用。在化学系化学催化项目的支持下，Sadow教授将探索一个化学领域，该领域已知的稀土甲硅烷基化合物相对较少，含有SiH基团的化合物更少。稀土金属-硅（[Ln]-SiR 3）化合物的大部分化学性质尚未探索。聚（氢化硅基）稀土化合物的最有利的反应途径，特别是消除和提取反应涉及的SiH部分的配体，将被发现，并将研究其机制。这些结构、键合和反应性问题的澄清将促进新的催化化学。更广泛的影响和教育计划是建立在一个坚实的理由，以增加本科专业的数量在爱荷华州，结合推广活动，这是值得称赞的。研究所建议为本科生开设一门课程，探讨职业问题，并激发他们对化学的兴趣。PI有一个化学教育的同事，伯内特博士在船上。对于从事这一研究项目的研究生，与奥地利格拉兹的格拉兹大学Marschner教授小组的合作将提供科学专门知识的国际交流。