Configuring first-row metal-metal bonded complexes to boost redox flexibility and N2 reduction activity

配置第一行金属-金属键合配合物以提高氧化还原灵活性和 N2 还原活性

• 批准号: 1800110
• 负责人: Connie Lu
• 金额: $ 42万
• 依托单位: University of Minnesota-Twin Cities
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-06-15 至 2021-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800110&HistoricalAwards=false
• 关键词: Configuring; first; row; metal; bonded

Nitrogen is essential to life and has many important uses including fertilizers, components of plastics, and ingredients of pharmaceuticals. Actually, nitrogen is abundant and easily accessible as it makes up 78% of the Earth's atmosphere. However, atmospheric nitrogen gas is very difficult to convert into forms that can be used for practical applications. In fact, the industrial conversion of atmospheric nitrogen into ammonia (the basic component of agricultural fertilizer and many industrial processes) utilizes extreme amounts of energy and the conversion of atmospheric nitrogen directly to a number of other industrial chemicals is not developed. In this project funded by the Chemical Synthesis program of the Chemistry Division, Professor Connie Lu of the University of Minnesota, Twin Cities is addressing these problems by developing ways to convert atmospheric nitrogen into chemicals other than ammonia. The methods utilize cobalt and iron compounds to transfer electrons to nitrogen. This activates the nitrogen and permits it be converted to a class of compounds know as amines, which are the basic building blocks for many industrially important chemicals. The project contains a strong educational component in which undergraduate and graduate students are trained for future careers in science and technology. Additionally, an outreach component provides experimental modules for middle and high-school students to teach topics of sustainability and catalysis.The redox processes available to first-row metal-metal bonded complexes can be more flexible than those of individual metals. This effect is seen in multi-metallic compounds, which are versatile catalysts for a broad range of organic and inorganic transformation. This property is utilized to prepare catalysts for the conversion of dinitrogen to amines. A series of bimetallic Co-M and Fe-M (M = Al, Ti, V, Cr, and Co) complexes are prepared and their redox flexibility characterized by synchrotron and theoretical methods. The ability of these species to catalyze the silylation of dinitrogen is investigated and the mechanism of this process is determined by chemical and theoretical studies. The goal is to devise catalytic N−C bond formation directly from dinitrogen. Throught these activities undergraduate and graduate students become skilled in syntheis, catalyst development, and mechanistic studies. A further outreach component targets middle and high school girls through experimentally based catalysis workshops.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.

氮对生命至关重要，具有许多重要用途，包括肥料、塑料成分和药品成分。事实上，氮含量丰富且易于获取，因为它占地球大气层的 78%。然而，大气中的氮气很难转化为可用于实际应用的形式。事实上，将大气中的氮工业转化为氨（农业肥料和许多工业过程的基本成分）需要消耗大量的能源，并且将大气中的氮直接转化为许多其他工业化学品的技术尚未开发出来。在这个由化学系化学合成项目资助的项目中，明尼苏达大学双城分校的 Connie Lu 教授正在通过开发将大气中的氮转化为氨以外的化学物质的方法来解决这些问题。该方法利用钴和铁化合物将电子转移到氮。这会激活氮并使其转化为一类被称为胺的化合物，胺是许多工业上重要化学品的基本组成部分。 该项目包含强大的教育内容，为本科生和研究生提供未来科学技术职业的培训。 此外，外展部分为中学生和高中生提供实验模块，教授可持续性和催化主题。第一排金属-金属键合络合物可用的氧化还原过程比单个金属的氧化还原过程更灵活。这种效应在多金属化合物中可见，多金属化合物是多种有机和无机转化的多功能催化剂。利用这一性质来制备将二氮转化为胺的催化剂。制备了一系列双金属 Co-M 和 Fe-M（M = Al、Ti、V、Cr 和 Co）配合物，并通过同步加速器和理论方法表征了它们的氧化还原灵活性。研究了这些物质催化二氮甲硅烷基化的能力，并通过化学和理论研究确定了该过程的机理。目标是设计直接从二氮形成催化 N−C 键。通过这些活动，本科生和研究生能够熟练掌握合成、催化剂开发和机理研究。进一步的外展部分通过基于实验的催化研讨会针对初中和高中女生。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力优点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

Enhanced Fe-Centered Redox Flexibility in Fe–Ti Heterobimetallic Complexes

• DOI: 10.1021/acs.inorgchem.9b00442
• 发表时间: 2019-04
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: James T Moore;S. Chatterjee;Maxime Tarrago;Laura J. Clouston;Stephen Sproules;E. Bill;Varinia Bernales;L. Gagliardi;Shengfa Ye;K. Lancaster;Connie C. Lu