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.

化学部化学综合计划的奖项支持Swarthmore学院的Christopher Graves教授的工作，以合成具有催化潜力的分子铝化合物。催化剂是引起化学反应发生的物质，并且在许多重要的实验室和工业过程中需要。由于催化剂通常基于稀有，昂贵的金属，因此发现含有常见，廉价金属的替代品很重要。在这方面，铝是其中最丰富，最便宜的元素之一。因此，它是用于催化的有吸引力的候选人。但是，有效的催化剂通常必须能够轻松获得和/或丢失电子，并且铝通常无法做到这一点。在这个项目中，通过将铝附加到能够获得和/或丢失电子的组上，可以解决问题。这导致基于铝的系统可以作为烯烃转化为烯烃（石油和天然气中的成分）为高价值化学物质的催化剂。此外，该项目为本科生提供了研究机会，这使他们准备进入劳动力或在研究生或专业学校中继续发展。最重要的是，学生们参加了费城科学节，并向当地和小学举办非洲裔美国人，西班牙裔和经济弱势群体的学生。在该项目中，铝协调了一系列多态硝基氧化物的基于硝基氧化物的配体，并结构和结合了结果的结构和结合。通过将多个N-O部分纳入在多种配体氧化态上存在的多齿状框架鲁棒络合物。通过配体取代基的变化，调节配合物的空间和电子性能，并评估它们激活小分子的能力。这些知识用于指导氧化铝氧化铝复合物的发展，作为烯烃抗马科夫尼科夫的催化剂。教育组成部分集中在本科生和外展计划的培训上，以K-12学生为目标。

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.