Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455-0431, United States.
J Am Chem Soc. 2020 Jul 8;142(27):11641-11646. doi: 10.1021/jacs.0c04937. Epub 2020 Jun 25.
A homogeneous rhodium-indium catalyst hydrodefluorinates substrates bearing strong aryl C-F bonds, including difluoro- and fluorobenzene, using 1 atm of H, alkoxide bases, and moderate temperatures (70-90 °C). Characterization of catalytic intermediates establishes a formal Rh/Rh redox cycle. The Rh → In interaction is proposed to enable catalysis by stabilizing the reactive Rh species, which is responsible for cleaving the Ar-F bond and is ultimately regenerated using H and base.
一种均相铑-铟催化剂在 1 个大气压的 H₂、烷氧基碱和中等温度(70-90°C)下,对具有强芳基 C-F 键的底物进行氢氟去氟化,包括二氟苯和氟苯。催化中间体的表征建立了一个形式上的 Rh/Rh 氧化还原循环。Rh→In 相互作用被认为可以通过稳定反应性 Rh 物种来实现催化,该物种负责断裂 Ar-F 键,并最终使用 H₂和碱再生。