Catalytic Metal-Mediated Small Molecule Fixation

催化金属介导的小分子固定

• 批准号: 1361716
• 负责人: Lawrence Sita
• 金额: $ 51.7万
• 依托单位: University of Maryland, College Park
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2014
• 资助国家: 美国
• 起止时间: 2014-07-01 至 2017-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1361716&HistoricalAwards=false
• 关键词: Catalytic; Metal; Mediated; Small; Molecule

With this award, the Chemical Catalysis Program in the Chemistry Division is funding Dr. Lawrence Sita from the University of Maryland to develop transition-metal catalysts that can be used for the production of high-value specialty chemicals from readily available, safe, and inexpensive starting materials, such as nitrogen, carbon dioxide, carbon monoxide, and sulfur. Advances in chemical technologies for the commercial production of high-value, industrial chemicals must be made in the near term in order to meet the increasing burdens placed on natural resources, energy, and the environment as the global population is anticipated to expand by 3 to 4 billion people over the next 50 years. In response to these needs, the primary objective of the project is the development of transition-metal catalysts that can be used to produce value-added, specialty chemicals from readily-available, inexpensive and safe starting materials, such as nitrogen, carbon dioxide, carbon monoxide, nitrous oxide and sulfur. The broader impact of this work is the potential development of more atom-economical and energy-efficient, industrial-scale chemical transformations that will be beneficial to the world economy, the environment, and the society and that can reduce the health- and security-risk of current technologies that require the generation, transportation, and on-site storage of hazardous reagents and intermediates. The proposed work will further provide an important vehicle by which future generations of undergraduates, graduate students, and postdoctoral researchers are trained.The focus of the research is the synthesis and characterization of mid-valent, second- and third-row, group 5 (Nb, Ta) and 6 (Mo, W) metal complexes with cyclopentadienyl amidinate (CPAM) and cyclopentadienyl guanidinate (CPGU) ligands. These complexes are suited for the study of the coordination and "fixation" of small molecules possessing X-Y multiple bonds (e.g., N2, O2, N2O, CO and CO2). The interaction between these metal complexes and the small molecules leads to (1) X-Y multiple bond cleavage compensated by the formation of strong M-X and M-Y bonding interactions, and (2) pathways for atom-economical, X- and Y-transfers to a substrate, which complete the catalytic cycle with respect to the starting metal complex. The CPAM and CPGU, molecularly-discrete complexes will be fully characterized both in solution using NMR, EPR, UV, and IR spectroscopies, electrospray mass spectrometry, and electrochemistry, and in the solid state using single-crystal X-ray analysis, elemental analyses, and IR and EPR spectroscopies.

有了这个奖项，化学部的化学催化计划是为马里兰州大学的劳伦斯·西塔（Lawrence Sita）博士提供资金，以开发过渡金属催化剂，可用于从易于获得，安全且廉价的起始材料（例如氮，二氧化碳，二氧化碳，碳一氧化碳和硫化）中生产高价值特色化学物质。 为了履行自然资源，能源和环境的增加，由于预计在未来50年内，全球人口将会扩大3至40亿人口，因此必须在短期内实现化学技术的进步，以实现工业化学品的商业生产，以实现工业化学物质。 为了满足这些需求，该项目的主要目的是开发过渡金属催化剂，这些催化剂可用于从易于利用，廉价且安全的起始材料中产生增值的特种化学物质，例如氮，二氧化碳，碳一氧化碳，一氧化碳，一氧化氮和硫磺。 这项工作的更广泛的影响是，更具原子经济和节能，工业规模的化学转化的潜在发展，这将对世界经济，环境和社会有益，并且可以减少需要发电，运输和现场存储危险的危险重点和中间体的当前技术的健康和安全风险。 The proposed work will further provide an important vehicle by which future generations of undergraduates, graduate students, and postdoctoral researchers are trained.The focus of the research is the synthesis and characterization of mid-valent, second- and third-row, group 5 (Nb, Ta) and 6 (Mo, W) metal complexes with cyclopentadienyl amidinate (CPAM) and cyclopentadienyl guanidinate (CPGU)配体。 这些复合物适用于具有X-Y多键的小分子的协调和“固定”（例如N2，O2，N2O，CO和CO2）。 这些金属络合物与小分子之间的相互作用导致（1）通过形成强的M-X和M-Y键相互作用来补偿的（1）X-Y多键裂解，以及（2）原子经济，X型和Y传递的途径，与底物相对于起始金属的催化循环。 使用NMR，EPR，UV和IR光谱，电喷雾质谱和电化学，以及使用单晶体X射线分析，元素分析，元素分析，以及IR和EPR EPPRoscopies。