Heterobimetallic Group 9 Complexes for C-F Bond Activation

用于 C-F 键活化的第 9 族异双金属配合物

• 批准号: 2102095
• 负责人: David Blank
• 金额: $ 50万
• 依托单位: University of Minnesota-Twin Cities
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-06-01 至 2025-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2102095&HistoricalAwards=false
• 关键词: Heterobimetallic; Group; Complexes; Bond; Activation

With this award, the Chemical Synthesis Program of the Division of Chemistry is supporting Professor Connie Lu of the University of Minnesota–Twin Cities, Department of Chemistry, to study organofluorine compounds; that is, chemical compounds that feature a carbon fluorine (C-F) bond. Organofluorine compounds are used as medicinal agents, insecticides, refrigerants, fire-fighting foam and stain-protective coatings for furniture and carpet. The C−F bond is especially strong and resistant to cleavage. As a consequence, organofluorines can persist and accumulate in the environment and physiologically. This project seeks ways to chemically degrade organofluorines by breaking the relatively unreactive C-F bonds and replacing all the F atoms with H atoms. The methods are to utilize rhodium and iridium catalysts to insert into the C-F bond, with molecular hydrogen serving as the reductant and H source. The project contains a strong educational component in which undergraduate and graduate students are trained for future careers in science and technology. For outreach, Dr. Lu will partner with science teachers at Antwatin Middle School with a majority of underrepresented students (50% African American, 26% Hispanic) to develop hands-on experiments related to energy and sustainability.Heterobimetallic Group 9 (Rh or Ir) complexes where the transition-metal has a formally zero or subvalent oxidation state and is braced are being investigated as reagents and catalysts for heat- or light-activated hydrodefluorination reactions. The metal centers in these Rh/Ir complexes are braced by sigma acceptor metalloligands and provide for electron rich character and engender enhanced nucleophilicity upon these metal centers thereby promoting C-F bond activation. The specific objectives of this project are to: (1) to synthesize and characterize heterobimetallic group 9 complexes bearing formal M(0) and M(-1) centers; (2) to investigate stoichiometric heat- and light-driven C-F bond activation facilitated by the heterobimetallic complexes; and, ultimately, and (3) to develop catalytic reactions that feature C-F bond activation as a key step. If successful, an important long term broader scientific impact of this research will reside in the development of fundamentally new chemistry to address the societal need to degrade pervasive perfluoroalkyl compounds.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.

有了这个奖项，化学系的化学合成计划正在支持明尼苏达大学双城分校化学系的Connie Lu教授研究有机氟化合物;即具有碳氟（C-F）键的化合物。 有机氟化合物可用作药剂、杀虫剂、制冷剂、灭火泡沫以及家具和地毯的防污涂料。C−F键特别牢固，不易断裂。因此，有机氟可以在环境和生理上持续存在和积累。该项目寻求通过破坏相对不活泼的C-F键并用H原子取代所有F原子来化学降解有机氟的方法。该方法是利用铑和铱催化剂插入C-F键，分子氢作为还原剂和H源。该项目包含一个强有力的教育组成部分，其中本科生和研究生接受培训，为未来的科学和技术职业。为了推广，陆博士将与Antwatin中学的科学教师合作，那里的大多数学生代表性不足（50%为非裔美国人，26%为西班牙裔），开展与能源和可持续性有关的实践实验。过渡金属具有形式上的零或低价氧化态并被支撑的（Rh或Ir）配合物正在被研究作为热反应的试剂和催化剂-或光活化的加氢脱氢反应。 这些Rh/Ir络合物中的金属中心由σ受体金属配体支撑，并提供富电子特性并在这些金属中心上产生增强的亲核性，从而促进C-F键活化。该项目的具体目标是：（1）合成和表征具有形式M（0）和M（-1）中心的第9族杂双金属配合物;（2）研究杂双金属配合物促进的化学计量热和光驱动的C-F键活化;最终，和（3）开发以C-F键活化为关键步骤的催化反应。如果成功的话，这项研究的一个重要的长期的更广泛的科学影响将存在于从根本上开发新的化学，以解决社会对降解普遍存在的全氟烷基化合物的需求。这个奖项反映了NSF的法定使命，并已被认为是值得通过使用基金会的智力价值和更广泛的影响审查标准进行评估的支持。