Platform-Supported Pairs of Lewis Acidic Metal Cations to Control and Catalyze Dinitrogen Functionalization

平台支持的路易斯酸性金属阳离子对控制和催化二氮官能化

• 批准号: 2154369
• 负责人: Polly Arnold
• 金额: $ 25.42万
• 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: 2022
• 资助国家: 美国
• 起止时间: 2022-08-01 至 2024-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2154369&HistoricalAwards=false
• 关键词: Platform; Supported; Pairs; Lewis; Acidic

With the support of the Chemical Synthesis (SYN) Program of the Chemistry Division, Professor Polly Arnold of the University of California–Berkeley, is studying the structure, bonding, and reactivity of f-block molecules with the long-term, ambitious goal of converting atmospheric nitrogen to ammonia and amines. Nitrogen gas (N2) is the major component of the atmosphere and potentially an inexpensive, chemically benign starting material for the industrial preparation of a vast variety of important chemical products. Currently, it is the feedstock for a single commercialized reaction, the Haber-Bosch process, which converts nitrogen to ammonia. This process is used on an enormous scale and provides the major source of nitrogen fertilizer worldwide. However, it functions at high temperatures and pressures, both consuming much energy and generating roughly 1% of global annual carbon dioxide emissions. Consequently, the discovery of more efficient processes to convert nitrogen to useful projects is extremely important. This project seeks to develop rare earth compounds that will mediate the conversion of nitrogen into ammonia and related compounds at low temperatures and pressures without generating carbon dioxide. The fundamental research proposed herein is expected to make fundamental contributions to important, unanswered questions about the chemical bonding in compounds composed of some of the heaviest atoms in the periodic table. It will also train members of the future workforce in the chemistry of the technology-critical rare earth elements, and in sustainable catalysis, both of which are high priority science areas for the nation.Under this award, the Arnold team will develop bimetallic rare earth and related Lewis acidic metal complexes supported by rigid tetraphenolate ligands with important and challenging goal of arriving at entries into the first catalytic conversion of dinitrogen N2 to secondary silylamines by a non-radioactive complex. The proposed program will work with specific lanthanides and co-reductants, according to their size, redox potentials, and Lewis acidity, to define the role of d- and f-orbitals in the stabilization of reduced intermediates and to enable the synthesis of new functionalized amines. Because electrons can be stored and transported through the ligand framework, the proposed program is also designed to tease apart metal/ligand contributions and develop new, lower-energy ways to deliver the reducing equivalents to the N2. The project will train students is the handling and manipulation of sensitive rare earth compounds and in the development of these into reagents for the reduction of small molecules.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.

在化学司的化学合成（SYN）计划的支持下，加利福尼亚大学 - 伯克利分校的Polly Arnold教授正在研究F-Block分子的结构，键合和反应性，其长期，雄心勃勃的目标是将大气氮转化为氨和弹药。氮气（N2）是大气的主要组成部分，可能是廉价的化学良性起始材料，用于工业制备各种重要的化学产品。目前，它是单个商业化反应的原料Haber-Bosch工艺，将氮转化为氨。该过程以巨大的规模使用，并为全球氮肥提供了主要来源。但是，它在高温和压力下起作用，既消耗了大量能量，又产生了大约1％的全球二氧化碳排放量。因此，发现更有效的过程以将氮转化为有用的项目非常重要。该项目旨在开发稀土化合物，以介导氮在低温和压力下不产生二氧化碳的氨和相关化合物的转化。预计本文提出的基本研究将对有关元素周期表中一些最重的原子组成的化合物中的化学键合成重要的，未解决的问题做出基本贡献。 It will Also train members of the future workforce in the chemistry of the technology-critical rare earth elements, and in sustainable catalysts, both of which are high priority science areas for the nation.Under this award, the Arnold team will develop bimetallic rare earth and related Lewis acidic metal complexes supported by rigid tetraphenolate ligands with important and challenge goal of arriving at entries into the first catalytic conversion of dinitrogen N2 to非放射活性复合物的二烯岛岛。提出的程序将根据特定的灯笼和共同还原剂，根据其大小，氧化还原电位和路易斯酸度，以确定D和F-轨道在稳定减少中间体中的作用，并启用新功能化胺的合成。由于可以通过配体框架存储和运输电子，因此拟议的程序还旨在教授金属/配体的贡献，并开发出新的，低能量的方法来提供与N2相同的减少等价物。该项目将培训学生是对敏感的稀土化合物的处理和操纵，并将其开发为减少小分子的试剂。该奖项反映了NSF的法定任务，并被认为是通过基金会的智力优点和更广泛的影响标准通过评估来评估的。