Unleashing phosphorus mononitride
- Simon Edin
- Christian Sandoval-Pauker
- Nathan J. Yutronkie
- Zoltan Takacs
- Fabrice Wilhelm
- Andrei Rogalev
- Balazs Pinter
- Kasper S. Pedersen
- Anders Reinholdt
2025-07-01
The interstellar diatomic molecule, phosphorus mononitride (P≡N), is highly unstable under conditions typical on Earth, and its utility for constructing elusive P–N π-bonded motifs has remained uncertain. Here, we show how Na(OCP) transfers a P atom to an electrophilic osmium nitride complex to form a metal-bound P≡N ligand. Quantum chemical calculations and X-ray absorption spectroscopy unveil a cumulenic [Os IV =N=P] electronic structure comprising orthogonal Os=N and N=P π-bonding. On reaction with elemental sulfur, the highly reduced P≡N ligand, formally [PN] 2– , forms a trigonal planar [NPS 2 ] 2– motif. Chlorination instead transforms the P≡N ligand to a bent [NPCl] – group coordinated to Os III ( S = ½). [3 + 2] cycloaddition of this radical with azide forms an aromatic interpnictide, [PN 4 ] – , that is inaccessible from the parent P≡N system. These findings provide a rare glimpse of the divergent reactivity of the alien P≡N molecule, paving the way to long-sought P–N multiple-bonded archetypes.