RUI: SusChem: Redox Active Aluminum Nitroxide Complexes for the anti-Markovnikov Hydrofunctionalization of Alkenes

该奖项由化学部化学合成项目颁发，支持斯沃斯莫尔学院克里斯托弗·格雷夫斯教授合成具有催化潜力的分子铝化合物的工作。催化剂是引起化学反应发生的物质，在许多重要的实验室和工业过程中都需要。由于催化剂通常是基于稀有、昂贵的金属，因此发现含有普通、廉价金属的替代品是很重要的。在这方面，铝是最丰富和最便宜的元素之一。因此，它是一个有吸引力的候选物用于催化。然而，有效的催化剂通常必须能够容易地获得和/或失去电子，而铝通常不能做到这一点。在这个项目中，通过将铝连接到能够获得和/或失去电子的基团上，可以避免这个问题。由此产生的铝基体系可以作为烯烃（石油和天然气中的成分）转化为高价值化学品的催化剂。此外，该项目为本科生提供了研究机会，为他们进入劳动力市场或在研究生或专业学校继续发展做好准备。除此之外，学生们还参加费城科学节，并向当地和有大量非裔美国人、西班牙裔和经济困难学生的小学伸出援手。在这个项目中，铝与一系列多齿氮基配体配位，并研究了所得到的配合物的结构和键合。通过将多个N-O基团结合到多齿状框架中，可以获得在配体氧化态范围内存在的强大配合物。通过配体取代基的变化，可以调节配合物的空间和电子性质，并评估其激活小分子的能力。这一知识用于指导开发铝-氮氧化物配合物作为烯烃的反马尔可夫尼科夫加氢功能化催化剂。教育部分集中在本科生的培训和面向K-12学生的拓展项目上。

This award by the Chemical Synthesis program of the Chemistry Division supports work by Professor Christopher Graves at Swarthmore College to synthesize molecular aluminum compounds that have catalytic potential. Catalysts are substances that cause a chemical reaction to occur and are required in many important laboratory and industrial processes. Since catalysts are often based on rare, expensive metals, the discovery of replacements that contain common, inexpensive metals is important. In this respect, aluminum is among the most abundant and least expensive of the elements. Consequently, it is an attractive candidate for use in catalysis. However, effective catalysts often must be able to easily gain and/or lose electrons and aluminum normally cannot do this. In this project, the problem is circumvented by attaching aluminum to groups that are capable of gaining and/or losing electrons. This results in aluminum based systems that can be developed as catalysts for the conversion of olefins (components in petroleum and natural gas) into high value chemicals. In addition, this project provides research opportunities for undergraduate students, which prepares them to enter the workforce or continue their development in graduate or professional schools. On top of this, the students participate in the Philadelphia Science Festival, and outreach to local and elementary schools with large populations of African American, Hispanic, and economically disadvantaged students.In this project aluminum is coordinated to a series of multi-dentate nitroxide-based ligands and the structure and bonding of the resulting complexes is studied. By incorporating multiple N-O moieties into a multi dentate framework robust complexes that exist over a range of ligand oxidation states are obtained. Through variations in ligand substituents the steric and electronic properties of the complexes are modulated and their ability to activate small molecules is evaluated. This knowledge is used to guide the development of aluminum-nitroxide complexes as catalysts for the anti-Markovnikov hydrofunctionalization of alkenes. An educational component centers on the training of undergraduate students and outreach programs targets K-12 students.