Lewis Acid-Mediated One-Electron Reduction of Nitrous Oxide

The one-electron reduction of nitrous oxide (N₂ O) was achieved using strong Lewis acids E(C₆ F₅ )₃ (E=B or Al) in combination with metallocenes. In the case of B(C₆ F₅ )₃ , electron transfer to N₂ O required a powerful reducing agent such as Cp*₂ Co (Cp*=pentamethylcyclopentadienyl). In the presence of Al(C₆ F₅ )₃ , on the other hand, the reactions could be performed with weaker reducing agents such as Cp*₂ Fe or Cp₂ Fe (Cp=cyclopentadienyl). The Lewis acid-mediated electron transfer from the metallocene to N₂ O resulted in cleavage of the N-O bond, generating N₂ and the oxyl radical anion [OE(C₆ F₅ )₃ ]^⋅- . The latter is highly reactive and engages in C-H activation reactions. It was possible to trap the radical by addition of the Gomberg dimer, which acts as a source of the trityl radical.