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

CAS：过渡金属-主族元素协同相互作用，实现新的化学转化

基本信息

批准号：
1954808
负责人：
Terry Tilley
金额：
$ 56.2万
依托单位：
University of California-Berkeley
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2020
资助国家：
美国
起止时间：
2020-08-01 至 2023-07-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1954808&HistoricalAwards=false
关键词：
CAS Transition Metal Main Group

项目摘要

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.

T.加州大学伯克利分校的唐蒂利（Don Tilley）由美国国家科学基金会化学部的化学合成项目资助，专注于合成含有金属和硅的化合物。这些物质在硅塑料、粘合剂、润滑剂和半导体等有用的硅基材料的生产中发挥着关键作用。新的金属硅化合物有望增强当前的应用，并支持新的硅基产品的发明。在一个项目中，蒂利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。总的来说，该计划是准备研究生和本科生的技术职业培训他们在尖端的化学技术以及沟通技巧。这笔赠款还用于支持对高中和小学学生的外联活动，目的是提高他们的技术知识，激发他们对科学的兴趣。这种推广包括口头介绍，演示和动手互动的经验教训。T.加州大学伯克利分校的Don蒂利，由国家科学基金会化学部的化学合成计划资助，探索了过渡金属络合物的合成，键合特性和反应化学，这些络合物具有与硅的多重键。在这些多重键合的物质中，亚甲硅烷基（LnM = SiRR '）和硅化物（[LnM] xSi; x = 2，3，4）络合物由于它们分别在（例如）硅氢化和硅材料合成中的作用而特别令人感兴趣。这些物种的广泛的金属-硅键合特征预计赋予不寻常的性能后，协调的硅片段，这些正在被利用来设计的研究和工业催化社区的强烈兴趣的反应催化剂。该计划的一个新主题是开发分子硅化物复合物的合成路线，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的一个未充分探索的领域。有关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、药物和甲硅烷基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，分子硅化物的研究提供了对有机硅生产中化学中间体的结构和反应性的深入了解（例如，直接法中的烷基氯硅烷）和硅纳米结构的合成。这项研究可能有助于化学家用来设计基本和工业相关的反应的知识基础。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，研究小组内部的合作努力涉及规划和向小学生提供科学课程。该奖项反映了NSF的法定使命，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，被认为值得支持。

项目成果

期刊论文数量（11）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Dimetalloylene (M‐E‐M) Complexes of Heavier Main Group Elements Ge, Sn, Pb, Bi via Cleavage of E‐X Bonds (X=N(SiMe 3 ) 2 , O t Bu) with an Iridium Hydride

通过 E-X 键 (X=N(SiMe 3 ) 2 , O t Bu) 与氢化铱断裂，形成较重主族元素 Ge、Sn、Pb、Bi 的二亚金属烯 (M-E-M) 配合物

DOI：
10.1002/chem.202301863
发表时间：
2023
期刊：
Chemistry – A European Journal
影响因子：
0
作者：
Saint‐Denis, Tyler G.;Zhang, Bowen;Settineri, Nicholas S.;Handford, Rex C.;Hall, Michael B.;Tilley, T. Don
通讯作者：
Tilley, T. Don

Switchable Product Selectivity in Diazoalkane Coupling Catalyzed by a Two-Coordinate Cobalt Complex

DOI：
10.1021/acscatal.1c02926
发表时间：
2021-09
期刊：
ACS Catalysis
影响因子：
12.9
作者：
Yuyang Dong;Michael I. Lipschutz;Ryan J. Witzke;J. Panetier;T. Tilley
通讯作者：
Yuyang Dong;Michael I. Lipschutz;Ryan J. Witzke;J. Panetier;T. Tilley

Bimetallic Mechanism for Alkyne Cyclotrimerization with a Two-Coordinate Fe Precatalyst

双配位 Fe 预催化剂的炔环三聚双金属机理

DOI：
10.1021/acscatal.0c01828
发表时间：
2020
期刊：
ACS Catalysis
影响因子：
12.9
作者：
Witzke, Ryan J.;Hait, Diptarka;Chakarawet, Khetpakorn;Head-Gordon, Martin;Tilley, T. Don
通讯作者：
Tilley, T. Don

Synthesis and Reactivity of a Dimeric Ni(I) Methyl Complex

二聚镍(I)甲基配合物的合成和反应活性