SusCHEM: Supramolecular Assembly and Catalysis Applications of Organoborane Polymers

SusCHEM：有机硼烷聚合物的超分子组装和催化应用

• 批准号: 1609043
• 负责人: Frieder Jaekle
• 金额: $ 43.5万
• 依托单位: Rutgers University Newark
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-09-15 至 2019-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1609043&HistoricalAwards=false
• 关键词: SusCHEM; Supramolecular; Assembly; Catalysis; Applications

In this project funded by the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry, Professor Frieder Jaekle of the Department of Chemistry at Rutgers University-Newark is studying a new class of polymers that contain the element, boron. Polymers are long chain organic molecules and are found in many facets of everyday life that utilize plastics, including food packaging, structural materials for automotive and aerospace transportation, and lightweight electronic devices. In this research project, Professor Jaekle is developing methods to synthesize polymers that contain specific boron-containing groups and then to utilize these polymers as catalysts for chemical reactions. Major features of these catalysts are that they are stable and easily recycled for further use. Professor Jaekle is training a diverse group of undergraduate and graduate students in a highly interdisciplinary research environment. The students are using and maintaining instrumentation for polymer research and education at Rutgers University-Newark. Professor Jaekle and his group are also involved in K-12 outreach activities and the stimulation of international scientific exchange through the organization of international symposia. Organoboranes are well-known for their Lewis acidic properties. When combined with hindered Lewis bases so-called "frustrated Lewis pairs" are generated that can be exploited in small molecule activation and in various catalytic processes. There are few examples of recyclable versions of these high-value catalysts, though. Professor Jaekle is studying how to attach functional organoboranes to both soluble polymers and polymer resins with easily accessible functional groups. Two target structures are being pursued: (1) highly electron-deficient triarylboranes that in concert with Lewis bases are capable of activating small molecules such as dihydrogen or silanes: These polymers will be tested as catalysts in the hydrogenation and hydrosilylation of imines, aldehydes and ketones. (2) electron-deficient borinic acids and corresponding polymers that are expected to display unusual self-assembly characteristics through hydrogen bonding and Lewis acid-base interactions: These polymers will be tested as catalysts in amidation reactions. Outreach activities involving K-12 students are being planned, including the participation of high school students from socio-economically disadvantaged backgrounds in research through the ACS Project SEED and the organization of Polymer and Materials Chemistry Outreach Programs that involve local schools with predominantly minority students.

在该项目中，由大分子，超分子和纳米化学计划在化学部门资助中，罗格斯大学 - 纽瓦克化学系教授弗里德·贾克尔（Frieder Jaekle）教授正在研究包含该元素的新聚合物。 聚合物是长链有机分子，在利用塑料的许多方面都可以发现，包括食品包装，用于汽车和航空航天运输的结构材料以及轻量级的电子设备。 在该研究项目中，Jaekle教授正在开发合成包含特定含硼基团的聚合物的方法，然后利用这些聚合物作为化学反应的催化剂。 这些催化剂的主要特征是它们稳定且容易回收以进一步使用。 Jaekle教授正在高度跨学科的研究环境中培训一群多元化的本科生和研究生。 学生正在罗格斯大学 - 纽瓦克使用和维护仪器进行聚合物研究和教育。 Jaekle教授及其小组还通过组织国际研讨会来参与K-12外展活动以及刺激国际科学交流。有机菜素以其刘易斯酸性特性而闻名。 当与阻碍的刘易斯基地结合使用时，即所谓的“沮丧的刘易斯对”将产生，可以在小分子激活和各种催化过程中被利用。但是，这些高价值催化剂的可回收版本几乎没有例子。 Jaekle教授正在研究如何将功能性有机烷源与可溶性聚合物和聚合物树脂一起使用易于访问的功能组。正在追求两个目标结构：（1）与刘易斯碱一起协同的高度电子缺陷的三级硼醇，能够激活诸如二氢或硅烷等小分子：这些聚合物将作为催化剂在氢化和氢化液中的催化剂中测试。 （2）通过氢键和刘易斯酸碱相互作用，预期将表现出异常的自组装特性的电子缺陷型硼酸和相应的聚合物：这些聚合物将在鉴定反应中作为催化剂进行测试。正在计划涉及K-12学生的外展活动，包括通过ACS Project SEED和聚合物和材料化学外展计划的组织中的社会经济不利背景的高中学生参与研究，这些计划涉及少数少数学生的当地学校。

项目成果

Electrophilic and nucleophilic displacement reactions at the bridgehead borons of tris(pyridyl)borate scorpionate complexes

三(吡啶基)硼酸酯蝎形配合物桥头硼的亲电和亲核置换反应

• DOI: 10.1039/d1cc06181j
• 发表时间: 2022
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Goura, Joydeb;McQuade, James;Shimoyama, Daisuke;Lalancette, Roger A.;Sheridan, John B.;Jäkle, Frieder
• 通讯作者: Jäkle, Frieder