SusCHEM: New Redox-Active Pincer Ligands for Sustainable Base Metal Cross Coupling Catalysis

有了这个奖项，化学系的化学催化计划资助格鲁吉亚理工学院的Jake Soper教授开发新的可持续，廉价和环境友好的催化剂，用于形成碳-碳键。选择性碳-碳键形成反应对于药物、特种和商品化学品、材料和燃料的合成是重要的。用于碳-碳键形成反应的大多数现有技术催化剂基于昂贵且稀有的贵金属，例如钯、铂和铱，并且碳-碳键的路线通常需要有毒或昂贵的前体分子。该项目通过开发基于更丰富和良性金属（如铁，钴和镍）的催化剂来解决这两个问题。为了实现这一目标，Soper教授的团队正在开发新的配体，以结合贱金属中心并赋予所需的反应性。研究小组包括高中生、本科生、研究生和高中化学教师。此外，一个教育推广计划正在为亚特兰大AP化学教室开发一系列在线教育模块，并附带演示，实验和课堂讨论。氧化还原活性配体可以在后期3d过渡金属上产生类似贵金属的有机金属反应。有了这个奖项，Soper教授正在准备新的钳型氧化还原活性配体，利用这些配体介导的氧化还原步骤进行功能性贱金属交叉偶联催化。目标反应包括钴催化的烷基醚亲电试剂的交叉偶联反应和铁、钴和镍催化的通过直接碳-氢活化的有氧分解性碳-碳交叉偶联反应。所有这些偶联反应通过用廉价且环境友好的贱金属催化剂代替钯，以及分别用双氧和碳-氢键代替含卤素的化学计量氧化剂和预官能化的底物来解决可持续性问题。

With this award, the Chemical Catalysis Program of the Division of Chemistry is funding Professor Jake Soper of the Georgia Institute of Technology to develop new sustainable, inexpensive and environmentally benign catalysts for the formation of carbon-carbon bonds. Selective carbon-carbon bond forming reactions are important for the synthesis of pharmaceuticals, specialty and commodity chemicals, materials, and fuels. Most state-of-the-art catalysts for carbon-carbon bond forming reactions are based on expensive and rare precious metals, such as palladium, platinum and iridium, and routes to carbon-carbon bonds often require toxic or expensive precursor molecules. This project is addressing both of these issues by developing catalysts based on more abundant and benign metals, such as iron, cobalt, and nickel. To accomplish this goal, Professor Soper's team is developing new ligands, to bind the base metal centers and impart the desired reactivity. The research team includes high school students, undergraduate students, graduate students, and high school chemistry teachers. In addition, an educational outreach program is developing a series of online education modules with accompanying demonstrations, experiments and in-class discussions for Atlanta AP chemistry classrooms.Redox-active ligands can bring about precious metal-like organometallic reactions at later 3d transition metals. With this award, Professor Soper is preparing new pincer-type redox-active ligands that harness these ligand-mediated redox steps for functional base metal cross coupling catalysis. Target reactions include cobalt-catalyzed cross coupling of alkyl ether electrophiles and iron, cobalt and nickel-catalyzed aerobic dehydrogenative carbon-carbon cross coupling via direct carbon-hydrogen activation. All of these coupling reactions address issues of sustainability by replacing palladium with base metal catalysts that are inexpensive and environmentally benign, as well as replacing halogen-containing stoichiometric oxidants and pre-functionalized substrates with dioxygen and carbon-hydrogen bonds, respectively.