苏黎世大学&萨尔大学最新Nature Chemistry | 光生三重态金氮烯用于金介导的氮烯转移!
TL;DR - A Nature Chemistry study reports the first structurally characterized terminal gold nitrene, photogenerated from a gold(III) azide. Its unusual electrophilic, nitrogen-centered diradical character establishes a new mechanistic basis for gold-mediated nitrogen-atom transfer.
- Crystallography, mass spectrometry, and calculations identify a triplet ground state with a nitrogen-centered diradical σ-bonded to gold(III).
- The nitrene activates O₂, inserts into intra- and intermolecular C–H bonds, captures CO, and undergoes alkyne addition/σ-rearrangement.
- The findings challenge gold-catalysis mechanisms that have traditionally excluded gold-nitrene intermediates.
- This work provides a conceptual platform for new C–N bond-forming and nitrogen-atom-transfer reactions.