Increasing the Electrophilicity at Boron via Carborane Substituents

通过碳硼烷取代基增加硼的亲电性

• 批准号: 2349851
• 负责人: Caleb Martin
• 金额: $ 57.5万
• 依托单位: Baylor University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2024
• 资助国家: 美国
• 起止时间: 2024-06-01 至 2027-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2349851&HistoricalAwards=false
• 关键词: Increasing; Electrophilicity; Boron; via; Carborane

With the support of the Chemical Synthesis program in the Division of Chemistry, Caleb Martin and his research team at Baylor University will study the synthesis of strong boron Lewis acids that feature non-conventional electron withdrawing substituents. Strong Lewis acids are essential to many important catalytic industrial and laboratory processes. Currently, boron compounds that contain fluorine are used in these reactions. However, there are pending Environmental Protection Agency mandates that will restrict the use of fluorine containing reagents that are set to begin 2025. Thus, replacements for the current boron-fluorine catalysts are essential. This project will develop an alternative to fluorine for boron-based catalysts for bond activation chemistry. This project also involves efforts to engage homeless high school students to stimulate their interest in science fields. Additionally, an annual advanced instrumentation workshop will host students and faculty from local small colleges.In this project, the Martin research team will synthesize boranes that feature icosahedral carborane clusters as electron withdrawing groups. A goal is to obtain boranes whose Lewis acidity is enhanced over that of their fluoroaryl counterparts. This enhancement will reflect electronic effects of the carborane substituent as well as the impact of carborane steric profiles upon the Lewis acid properties of these new boron-centered systems. The bulk and Lewis acidity of tris(ortho-carboranyl)borane will be investigated in frustrated Lewis pair chemistry. The other target, bis(1-methyl-ortho-carboranyl)borane, features a highly polar B-H bond. The reactivity of this bond as well as the stability of aryl variants will be studied. The proposed work will investigate the reactivity and properties of the newly synthesized borane Lewis super-acids. If successfully, the development of such new classes of non-fluorine-based boron-centered Lewis acids, could have a broad impact on synthetic and mechanistic chemistry, with implications for sustainable chemistry.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在化学合成计划中，贝勒大学的Caleb Martin和他的研究团队的支持下，将研究具有非惯性电子撤出取代基的强硼刘易斯酸的合成。强刘易斯酸对于许多重要的催化工业和实验室过程至关重要。当前，在这些反应中使用了含有氟的硼化合物。但是，有一个未决的环境保护机构的要求，将限制使用含氟的试剂的使用。因此，当前的硼氟氟催化剂的替换是必不可少的。该项目将开发氟氟基于硼基的催化剂的替代方案，用于键化化学。该项目还涉及努力吸引无家可归的高中生刺激他们对科学领域的兴趣。此外，年度高级仪器研讨会将接待当地小型学院的学生和教职员工。在该项目中，马丁研究小组将合成以二十面体卡伯兰群集为电子撤离组的硼烷。一个目标是获得硼烷，其氟化液的酸味性增强了。这种增强将反映Carborane取代基的电子效应，以及Carborane空间轮廓对这些新的以硼中心系统的刘易斯酸性能的影响。 Tris（Ortho-Carboranyl）硼烷的散装和刘易斯酸度将在沮丧的刘易斯对化学中进行研究。另一个靶BI（1-甲基 - 碳碳烷基）硼烷具有高极性B-H键。将研究该键的反应性以及芳基变体的稳定性。拟议的工作将研究新合成的Borane Lewis Super-Acids的反应性和特性。如果成功的话，以以可持续性化学的影响对合成和机械性化学产生了广泛的影响，则可以开发此类新类别的非氟硼氨酸以硼的刘易斯酸的影响，这对可持续性化学产生了影响。该奖项反映了NSF的法定任务，并被认为是通过基金会的智力优点和广泛影响的评估来评估的支持。