CAS: Transition Metal-Main Group Element Cooperative Interactions to Enable New Chemical Transformations

加州大学伯克利分校的T.Don Tilley教授的研究项目由国家科学基金会化学部化学合成计划资助，重点是合成同时含有金属和硅的化合物。这些物质在生产有用的硅基材料，如硅塑料、粘合剂、润滑剂和半导体中发挥着关键作用。新的金属-硅化合物有望增强当前的应用，并为新的硅基产品的发明奠定基础。在一个项目中，Tilley正在研究一类新的化合物，其特征是硅原子夹在一对金属离子之间。另一个项目是探索用铁替代铂制造有机硅的可能性。总体而言，该项目通过对研究生和本科生进行尖端化学技术和沟通技能培训，为他们的技术职业生涯做好准备。这笔赠款还支持向高中生和小学生提供服务，目的是提高他们的技术知识，激发他们对科学的兴趣。这一推广活动包括口头演示、演示和动手互动课程。加州大学伯克利分校T.Don Tilley教授的研究项目由美国国家科学基金会化学部化学合成计划资助，探索具有多个硅键的过渡金属络合物的合成、成键性质和反应化学。在这些多键物种中，硅烯(LNM=SiR‘)和硅化物([LNM]xSi；x=2，3，4)络合物因其在(例如)硅氢化和硅材料合成中的作用而特别令人感兴趣。这些物种所具有的广泛的金属-硅键有望赋予配位硅片段不寻常的性质，这些特性正被用于设计引起研究和工业催化界强烈兴趣的活性催化剂。该计划中的一个新主题是开发合成分子硅化物络合物的路线，以及探索新硅化物的化学性质。这些稀有物种代表了过渡金属主族研究中一个未被开发的领域。分子硅化物化学的基本问题对先进硅材料和工艺的发展具有重要意义。更广泛地说，这项研究为与生产硅材料、聚合物、药物、硅烷化原料和特种化学品的化学转化相关的新战略提供了基础。特别是，对分子硅化物的研究提供了对有机硅生产(例如，直接工艺中的烷基氯硅烷)和硅纳米结构合成中的化学中间体的结构和反应性的洞察。这项研究可能有助于化学家用来设计从根本上和工业上相关的反应的知识库。由于这项研究使用了广泛的合成和光谱技术，通过该计划培训的科学家成为高效的研究人员。值得注意的是，研究小组内部的一项合作努力包括计划和向小学生提供科学课程。小组成员前往附近的小学教授基本科学原理，希望改善早期STEM教育并鼓励初出茅庐的科学家。该奖项反映了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。

The research program of Professor T. Don Tilley at the University of California, Berkeley, funded by the Chemical Synthesis Program of the Division of Chemistry within the National Science Foundation, focuses on the synthesis of chemical compounds that contain both metals and silicon. These substances play key roles in the production of useful silicon-based materials, such as silicone plastics, adhesives, lubricants, and semiconductors. New metal-silicon compounds promise to enhance current applications and underpin the invention of new silicon-based products. In one project, Tilley is studying a new class of compounds that feature silicon atoms sandwiched between a pair of metal ions. Another project is exploring the possible replacement of platinum with iron for making silicones. Overall, this program is preparing graduate and undergraduate students for technical careers by training them in cutting edge chemical techniques as well as in communication skills. This grant is also supporting outreach to students in high school and elementary schools with the goal of enhancing their technical knowledge and stimulating their interests in science. This outreach involves oral presentations, demonstrations, and hands-on interactive lessons. The research program of Professor T. Don Tilley at the University of California, Berkeley, funded by the Chemical Synthesis Program of the Division of Chemistry within the National Science Foundation, explores the synthesis, bonding properties, and reaction chemistry of transition-metal complexes featuring multiple bonds to silicon. Of these multiply bonded species, silylene (LnM=SiRR’) and silicide ([LnM]xSi; x = 2,3,4) complexes are of particular interest due to their roles in (for example) hydrosilations and silicon materials synthesis, respectively. The extensive metal-silicon bonding featured by these species is expected to impart unusual properties upon the coordinated silicon fragments, and these are being exploited to design reactive catalysts of strong interest to the research and industrial catalysis communities. A novel theme within this program is the development of synthetic routes leading to molecular silicide complexes, as well as the exploration of chemical properties for the new silicides. These rare species represent an underexplored area of transition metal-main group research. Fundamental questions regarding molecular silicide chemistry have important implications for the development of advanced silicon materials and processes. More broadly, this research provides a foundation for new strategies relating to chemical transformations that produce silicon materials, polymers, drugs, and silylated feedstock and specialty chemicals. In particular, the study of molecular silicides provides insights into the structure and reactivity of chemical intermediates in silicones production (e.g., alkylchlorosilanes in the Direct Process) and in the synthesis of silicon nanostructures. This research may contribute to the knowledge base that chemists use to design reactions that are fundamentally and industrially relevant. Because this research uses a broad array of synthetic and spectroscopic techniques, the scientists trained through this program emerge as highly effective researchers. Notably, a collaborative effort within the research group involves planning and presenting science lessons to grade school students. Group members travel to nearby elementary schools and teach basic scientific principles, hoping to improve early STEM education and encourage budding scientists.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.