N-Heterocyclic Carbenes in the Synthesis of Reactive Small Clusters of Group 11 Metals

N-杂环卡宾在第 11 族金属反应性小团簇合成中的应用

• 批准号: 1300659
• 负责人: Joseph Sadighi
• 金额: $ 43.63万
• 依托单位: Georgia Tech Research Corporation
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-09-15 至 2017-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1300659&HistoricalAwards=false
• 关键词: Heterocyclic; Carbenes; Synthesis; Reactive; Small

With this award from the Chemical Synthesis (SYN) Program, Professor Joseph Sadighi at the Georgia Institute of Technology will study reactive N-heterocyclic carbene (NHC) compounds having dinuclear and trinuclear copper, silver and gold species. The NHC ligand will support a trinuclear gold cation, in which metal-metal bonding results primarily from s-orbital interactions, as well as hydride-bridged dinuclear cations displaying varying degrees of metal-metal bonding. This research will include the tuning of trigold clusters to develop multielectron redox reactions, and the synthesis of analogous complexes such as tricopper and trisilver cations with the ultimate goal of having such compounds serve as platforms for the development of catalytic reactions. Dinuclear and trinuclear metal-element clusters, formed through atom- or group-transfer reactions, will be studied, and the synthesis of reactive metal hydride complexes through dihydrogen activation will be developed. Finally, the stabilization of odd-electron complexes with fractional metal-metal bonding will be explored.This research is designed to afford insight into unusual types of bonding among metal centers, or between metals and main group elements. Unusual bonding motifs can be tailored to enable normally difficult bond-breaking and bond-forming processes. Control of these processes is crucial to the development of new catalysts for such important and challenging reactions as the controlled oxidation of hydrocarbons, using oxygen from the atmosphere, or the conversion of carbon dioxide or carbon monoxide into liquid fuels. This is expected to contribute to sustainable chemistry. The graduate and undergraduate students who carry out this research will be prepared to contribute to the future of science in the United States as academic researchers and teachers, or as research scientists in chemical industry or in government laboratories. The research team will reach out to local high schools, to identify interested students from Atlanta's diverse student body and to give them the experience of research in the university setting.

获得化学合成（SYN）项目的奖金后，乔治亚理工学院的Joseph Sadighi教授将研究具有双核和三核铜、银和金的活性n -杂环碳（NHC）化合物。NHC配体将支持三核金阳离子，其中金属-金属键主要由s轨道相互作用产生，以及氢化物桥接的双核阳离子显示不同程度的金属-金属键。这项研究将包括调整三old簇以发展多电子氧化还原反应，以及合成类似的配合物，如三铜和三银阳离子，最终目标是让这些化合物作为发展催化反应的平台。将研究通过原子或基团转移反应形成的双核和三核金属元素团簇，并将开发通过双氢活化合成活性金属氢化物配合物。最后，探讨了具有分数金属-金属键的奇电子配合物的稳定性。这项研究旨在深入了解金属中心之间或金属与主要族元素之间的不寻常类型的键合。可以定制不寻常的键合图案，以实现通常困难的键断和键形成过程。控制这些过程对于开发新的催化剂至关重要，这些催化剂用于诸如碳氢化合物的可控氧化、利用大气中的氧气或将二氧化碳或一氧化碳转化为液体燃料等重要和具有挑战性的反应。这有望为可持续化学做出贡献。进行这项研究的研究生和本科生将准备作为学术研究人员和教师，或作为化学工业或政府实验室的研究科学家，为美国科学的未来做出贡献。研究小组将接触到当地的高中，从亚特兰大多样化的学生群体中找出感兴趣的学生，并为他们提供在大学环境中进行研究的经验。