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.

在这个由化学系大分子，超分子和纳米化学项目资助的项目中，罗格斯大学纽瓦克分校化学系的Frieder Jaekle教授正在研究一类含有硼元素的新型聚合物。 聚合物是长链有机分子，存在于日常生活中使用塑料的许多方面，包括食品包装，汽车和航空航天运输的结构材料以及轻质电子设备。 在这个研究项目中，Jaekle教授正在开发合成含有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点是它们是稳定的，易于回收再利用。 Jaekle教授正在高度跨学科的研究环境中培养多样化的本科生和研究生。 学生们正在使用和维护罗格斯大学纽瓦克分校的聚合物研究和教育仪器。 Jaekle教授和他的小组还参与K-12外展活动，并通过组织国际研讨会促进国际科学交流。有机硼烷因其刘易斯酸性质而众所周知。 当与受阻刘易斯碱结合时，产生所谓的“受抑刘易斯对”，其可用于小分子活化和各种催化过程。然而，这些高价值催化剂的可回收版本的例子很少。 Jaekle教授正在研究如何将功能性有机硼烷连接到具有容易获得的官能团的可溶性聚合物和聚合物树脂上。两种目标结构正在研究中：（1）高度缺电子的三芳基硼烷，与刘易斯碱一起能够活化小分子，如二氢或硅烷：这些聚合物将在亚胺、醛和酮的氢化和氢化硅烷化中作为催化剂进行测试。 (2)预计通过氢键和刘易斯酸碱相互作用显示出不寻常的自组装特性的缺电子硼酸和相应的聚合物：这些聚合物将作为酰胺化反应中的催化剂进行测试。目前正在规划涉及K-12学生的外联活动，包括通过ACS项目SEED和组织聚合物和材料化学外联方案，让来自社会经济弱势背景的高中生参与研究，这些方案涉及以少数民族学生为主的当地学校。

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