Trimethylsilyl-Induced N–O Bond Cleavage in Nitrous Oxide-Derived Aminodiazotates

The chemical activation of nitrous oxide (N₂O) typically results in O-atom transfer and the extrusion of N₂ gas. In contrast, reactions of N-trimethylsilyl (TMS)-substituted amides with N₂O give inorganic or organic azides, with concomitant formation of silanols or siloxanes. N-TMS-substituted amides are also able to induce N–O bond cleavage in N₂O-derived dialkylaminodiazotates, generating tetrazene salts. These results indicate the potential of silyl groups in devising transformations, in which N₂O acts as an N-atom donor.