CAS: Organometallic Chemistry of Catalytically Relevant High Valent Nickel and Copper

通过这一奖项，美国国家科学基金会化学部的化学催化计划支持了密歇根大学化学系的Melanie Sanford教授研究镍和铜催化剂用于制造有机分子的基本反应性。过渡金属催化剂被用来制造许多重要的产品，包括挽救生命的药物、保护作物的农用化学品和电子材料。这些产品的成本和可持续性直接受到新催化剂开发的影响，这些催化剂更便宜，产生的废物更少，并且在更温和的反应条件下操作。一个特别重要的目标是用来自廉价和更容易获得的金属(例如镍和铜)的催化剂取代需要稀有和昂贵贵金属(例如钯)的催化剂。最近在这方面取得了许多令人振奋的进展，但这些价格较低的催化剂的性能仍然落后于贵金属催化剂。为了解决他的问题，需要更好地了解廉价催化剂的基本反应性。桑福德教授和她的研究小组正在研究镍和铜催化剂的反应性，以确定如何使这些化合物在加快合成所需有机分子方面的表现与贵金属类似物一样或更好。外展活动旨在通过桑福德教授和她的研究小组参加辅导研讨会、小组讨论和密歇根大学女性在数学、工程和科学方面表现更出色的项目(FEMMES)，鼓励女性参与不同层次的STEM领域。第一排过渡金属催化的有机分子合成工艺的开发最近出现了热潮。围绕这些转变的兴奋源于设计地球丰富且廉价的催化剂支架的可持续性优势，以及第一排过渡金属络合物可访问的独特反应模式。尽管已经报道了许多重要的镍和铜催化的交叉偶联反应和C-H官能化反应，但涉及这些转化的金属有机化合物镍(III)、镍(IV)和铜(III)的合成和基本反应活性尚未得到系统的研究。Sanford教授和她的研究小组正在努力建立在镍(III)、镍(IV)和铜(III)中心使用直接基团配位底物以及由氨基喹啉配体支持的非定向过程进行各种转化的可行性和机制。这里建立的反应性和选择性分布有望对新的高价镍和铜催化转化的设计和优化产生变革性的影响。该项目还在无机和有机合成、无机反应机理和催化等跨学科领域培训一批不同的研究生和本科生。一支训练有素、多元化的科学队伍对于21世纪先进制造业创新和技术的持续进步至关重要。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 this award, the Chemical Catalysis Program of the NSF Division of Chemistry is supporting the research of Professor Melanie Sanford of the Department of Chemistry at the University of Michigan to study the fundamental reactivity of nickel and copper catalysts for making organic molecules. Transition metal catalysts are used to manufacture many important products, including life-saving pharmaceuticals, crop-protecting agrochemicals, and electronic materials. The cost and sustainability of these products are directly impacted by the development of new catalysts that are less expensive, generate less waste, and operate under milder reaction conditions. A particularly important goal is to replace catalysts that require rare and expensive precious metals (e.g. palladium) with catalysts derived from inexpensive and more readily available metals (e.g. nickel and copper). Many exciting advances have recently been made in this direction, but the performance of these less expensive catalysts still lags behind precious metal catalysts. To fix his problem, the fundamental reactivity of the inexpensive catalysts needs to be better understood. Professor Sanford and her research group are studying the reactivity of nickel and copper catalysts to determine how to make these compounds perform as well or better than precious metal analogues in speeding up the synthesis of desired organic molecules. Outreach activities are directed towards encouraging women to engage in STEM fields at a variety of levels through the participation of Professor Sanford and her research group in mentoring workshops, panel discussions, and the University of Michigan Females Excelling More in Mathematics, Engineering, and Science (FEMMES) program, which introduces middle school girls to hands-on science.The development of first row transition metal catalyzed processes for the synthesis of organic molecules has recently had an upsurge in activity. Excitement surrounding these transformations stems from the sustainability advantage of designing earth abundant and inexpensive catalyst scaffolds, as well as the unique reactivity patterns accessible to first row transition metal complexes. Despite the number of important nickel- and copper-catalyzed crossing coupling and C-H functionalization reactions that have been reported, the synthesis and fundamental reactivity of the organometallic nickel(III), nickel(IV), and Cu(III) compounds implicated in these transformations have not been systematically explored. Professor Sanford and her research group are working to establish the feasibility and mechanisms of a variety of transformations at nickel(III), nickel(IV), and copper(III) centers using directing group coordinated substrates, as well as undirected processes supported by aminoquinoline ligands. The reactivity and selectivity profiles that are being established herein are expected to have a transformative impact on the design and optimization of new high valent nickel- and copper-catalyzed transformations. This project is also training a diverse group of graduate and undergraduate students in the interdisciplinary areas of inorganic and organic synthesis, inorganic reaction mechanisms, and catalysis. A well-trained and diverse scientific workforce is essential for continued advances in advanced manufacturing innovation and technology in the 21st century.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.