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<p>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<sup>IV</sup>=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]<sup>2–</sup>, forms a trigonal planar [NPS<sub>2</sub>]<sup>2–</sup> motif. Chlorination instead transforms the P≡N ligand to a bent [NPCl]<sup>–</sup> group coordinated to Os<sup>III</sup> (<i>S</i> = ½). [3 + 2] cycloaddition of this radical with azide forms an aromatic interpnictide, [PN<sub>4</sub>]<sup>–</sup>, 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.</p>

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Unleashing phosphorus mononitride

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年7月1日

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  • Simon Edin,
  • Christian Sandoval-Pauker,
  • Nathan J. Yutronkie,
  • Zoltan Takacs,
  • Fabrice Wilhelm,
  • Andrei Rogalev,
  • Balazs Pinter,
  • Kasper S. Pedersen,
  • Anders Reinholdt

摘要

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.