Unleashing phosphorus mononitride

Simon Edin, Christian Sandoval-Pauker, Nathan J. Yutronkie, Zoltan Takacs, Fabrice Wilhelm, Andrei Rogalev, Balazs Pinter, Kasper S. Pedersen () and Anders Reinholdt ()
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Simon Edin: Lund University
Christian Sandoval-Pauker: University of Texas at El Paso
Nathan J. Yutronkie: CS 40220
Zoltan Takacs: Lund University
Fabrice Wilhelm: CS 40220
Andrei Rogalev: CS 40220
Balazs Pinter: University of Texas at El Paso
Kasper S. Pedersen: Technical University of Denmark
Anders Reinholdt: Lund University

Nature Communications, 2025, vol. 16, issue 1, 1-12

Abstract: Abstract 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 [OsIV=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 [NPS2]2– motif. Chlorination instead transforms the P≡N ligand to a bent [NPCl]– group coordinated to OsIII (S = ½). [3 + 2] cycloaddition of this radical with azide forms an aromatic interpnictide, [PN4]–, 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.

Date: 2025
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DOI: 10.1038/s41467-025-60669-6

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