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

RUI：SusChem：氧化还原活性氮氧化铝配合物用于烯烃的抗马可夫尼科夫氢功能化

• 批准号: 1664902
• 负责人: Christopher Graves
• 金额: $ 17.4万
• 依托单位: Swarthmore College
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-07-01 至 2021-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1664902&HistoricalAwards=false
• 关键词: RUI; SusChem; Redox; Active; Aluminum

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.

化学部化学合成项目的这一奖项支持了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。由于催化剂通常基于稀有、昂贵的金属，因此发现含有常见、廉价金属的替代品非常重要。在这方面，铝是最丰富和最便宜的元素之一。因此，它是用于催化的有吸引力的候选者。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来规避这个问题。这导致铝基系统可以被开发为用于将烯烃（石油和天然气中的组分）转化为高价值化学品的催化剂。此外，该项目为本科生提供研究机会，为他们进入劳动力市场或在研究生院或专业学校继续发展做好准备。除此之外，学生们还参加了费城科学节（Philadelphia Science Festival），并深入到当地和小学，那里有大量的非裔美国人、西班牙裔和经济困难的学生。在这个项目中，铝与一系列多齿氮氧配体配位，并研究了所得配合物的结构和键合。通过将多个N-O部分并入到多齿框架中，获得了在一系列配体氧化态下存在的稳健络合物。通过配体取代基的变化，调节络合物的空间和电子性质，并评估其活化小分子的能力。这方面的知识是用来指导开发的铝-氮氧化物配合物作为催化剂的反马尔可夫氢官能化的烯烃。教育部分集中在本科生的培训和推广计划的目标K-12学生。

项目成果

Synthesis and Characterization of (pyNO−)2GaCl: A Redox-Active Gallium Complex

(pyNO-)2GaCl：氧化还原活性镓配合物的合成和表征

• DOI: 10.3390/inorganics6020050
• 发表时间: 2018
• 期刊: Inorganics
• 影响因子: 2.9
• 作者: Kirsh, Jacob;Woodside, Audra;Manor, Brian;Carroll, Patrick;Rablen, Paul;Graves, Christopher
• 通讯作者: Graves, Christopher

Synthesis and Characterization of a Tripodal Tris(nitroxide) Aluminum Complex and Its Catalytic Activity toward Carbonyl Hydroboration

三足三(硝基氧)铝配合物的合成、表征及其对羰基硼氢化反应的催化活性

• DOI: 10.1021/acs.organomet.8b00933
• 发表时间: 2019
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Woodside, Audra J.;Smith, Mackinsey A.;Herb, Thomas M.;Manor, Brian C.;Carroll, Patrick J.;Rablen, Paul R.;Graves, Christopher R.
• 通讯作者: Graves, Christopher R.