Inorganic Chemistry

Taming Phosphorus Mononitride (PN)



Phosphorus mononitride (PN) only has a fleeting existence on Earth and molecular precursors for a mild release of the molecule to enable chemical synthesis in solution do not exist. Here we report the synthesis of an anthracene (A) based molecular precursor (N3PA) that dissociates into dinitrogen (N2), A and PN in solution with a first order half-life of roughly t 1/2 = 30 min at room temperature associated with an activation enthalpy of ΔH ⧧ = 19.5 ± 1.7 kcal mol –1 and an activation entropy of ΔS ⧧ = −8.8 ± 0.8 cal mol –1 K –1 . Heated under vacuum N3PA decomposes in an explosive fashion at around 42 °C as demonstrated in a molecular beam mass spectrometry (MBMS) study. N3PA serves as a PN transfer reagent as demonstrated in the synthesis of [(dppe)Fe(Cp*)(NP)][BArF24]. Surprisingly, the terminal N-bonded linkage isomer is energetically preferred due to significant covalent iron pnictogen bond character and associated less unfavorable Pauli repulsion in the metal-ligand interaction.


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Supplementary material

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Supporting Information – Taming Phosphorous Mononitride (PN)
NMR and IR Spectra, Monitoring the Decay of N3PA by 1H NMR Spectroscopy, Molecular Beam Mass Spectrometry (MBMS), Mößbauer Spectroscopy, X-Ray Diffraction Studies, Computational Studies, References and Full Citations for Electronic Structure Codes.