Constructing Metal-Carbon Multiple Bonds for Dehydrogenation and Dehydrocoupling Reactions Involving Volatile Hydrocarbons

在化学部合成计划的资助下，宾夕法尼亚大学的Daniel Mindiola博士的研究小组正在研究合成含有钛、Nb和钒的富含地球的(即“碱”)金属络合物。研究了这些配合物在温和条件下催化转化为烯烃(即具有碳-碳双键的化合物)的能力。烯烃是工业中的积木，可用于构建聚合物或制药和石化产品所必需的其他商品化学品。研究小组还在研究如何将天然气或挥发性自然资源转化为液体燃料，因为这些燃料更容易运输和储存。该团队还在研究如何将大气中的氮转化为化学燃料和重要的试剂，如氨或铵盐。这是在温和的条件下完成的，也使用了定义良好的贱金属催化剂。该团队正在合成的催化剂在比石化工业中使用的裂化条件(800摄氏度)温和的条件下发挥作用。明迪奥拉博士一直活跃在美国化学学会，担任美国化学学会学者计划少数民族事务小组委员会主席，以及促进物理科学多样性的许多其他活动。他积极参与在该地区的大学和中小学推广科学，进行旨在了解氮气和天然气等自然资源的演示。Mindiola正在研究在C4及以上的情况下，钛、钒和Nb等碱性、早期过渡金属如何促进挥发性和直线型碳氢化合物选择性地转移脱氢为烯烃和末端烯烃。研究小组正在调查温和的条件，通过利用金属-碳多键的活性性质来执行这种转化。通过合成和机理研究，该团队正在探索优化条件，以获得更高的催化剂周转率和选择性。一种特殊的反应是使用定义明确的亚烷基钛或坚固的双核体系将甲烷在室温下转化为烯烃。明迪奥拉博士还在探索利用贱金属Nb前体将大气中的氮在室温下催化转化为氨和铵盐，这些前体易于制备和处理，并产生了中间体，为这些系统如何结合、激活和裂解N-N三键提供了线索。明迪奥拉博士通过旨在促进物理科学多样性的委员会和小组委员会，积极参与美国化学学会的工作。他还积极参与大学和他所在的社区，促进有关天然气和其他温室气体的科学和教育社会。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With funding from the Synthesis Program of the Chemistry Division, the research team of Dr. Daniel Mindiola at the University of Pennsylvania is investigating the synthesis of earth-abundant (i.e., "base") metal complexes containing titanium, niobium, and vanadium. The complexes are studied for their ability to convert, catalytically and under mild conditions, alkanes into alkenes (i.e., compounds with carbon-carbon double bonds). Alkenes are building blocks in industry and are useful in the construction of polymers or other commodity chemicals indispensable to pharmaceuticals and petrochemicals. The research team is also investigating how to convert natural gas or volatile natural resources into liquid fuels since these are much easier to transport and store. The team is also investigating ways to convert nitrogen from our atmosphere into chemical fuels and important reagents such as ammonia or ammonium salts. This is done under mild conditions, also using well defined base metal catalysts. The catalysts that the team is synthesizing function under conditions that are milder (70-80 degree C) than cracking conditions used in the petrochemical industry (800 degree C). Dr. Mindiola has been active with the ACS (American Chemical Society) serving as Chair of the ACS Scholars Program Subcommittee on Minority Affairs among many other activities to promote diversity in the physical sciences. He is actively involved in promoting science at the university level as well as in elementary and middle schools in the region by conducting demonstrations aimed at understanding natural resources such as nitrogen and natural gas.Dr. Mindiola is investigating how base, early transition metals such as Ti, V, and Nb can promote the transfer dehydrogenation of volatile and linear hydrocarbons, selectively, into olefins and terminal olefins in the case of C4 and above. The research team is investigating mild conditions to perform such transformations by taking advantage of the reactive nature of metal-carbon multiple bonds. Through synthetic and mechanistic studies, the team is exploring optimization of conditions for higher catalytic turnover and selectivity. One particular reaction is the room temperature conversion of methane into an olefin using a well-defined Ti alkylidene or robust dinuclear systems. Dr. Mindiola is also exploring the catalytic room temperature conversion of atmospheric nitrogen into ammonia and ammonium salts using base metal niobium precursors that are simple to prepare and handle, and which have yielded intermediates that provide clues into how these systems bind, activate, and split the N-N triple bond. Dr. Mindiola is heavily involved with the American Chemical Society through committees and subcommittees aimed at promoting diversity in the physical sciences. He is also actively involved at the university level and in his community promoting science and educating society about natural gas and other greenhouse gases.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.