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Journal Article

Taming phosphorus mononitride


Bistoni,  Giovanni
Research Group Bistoni, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Eckhardt, A. K., Riu, M.-L.-Y., Ye, M., Müller, P., Bistoni, G., & Cummins, C. C. (2022). Taming phosphorus mononitride. Nature Chemistry, 14(8), 928-934. doi:10.1038/s41557-022-00958-5.

Cite as: https://hdl.handle.net/21.11116/0000-000A-FF65-6
Phosphorus mononitride (PN) only has a fleeting existence on Earth, and molecular precursors for the release of this molecule under mild conditions in solution have remained elusive. Here we report the synthesis of an anthracene-based precursor—an anthracene moiety featuring an azidophosphine bridge across its central ring—that dissociates into dinitrogen, anthracene and P≡N in solution with a first-order half-life of roughly 30 min at room temperature. Heated under reduced pressure, this azidophosphine–anthracene precursor decomposes in an explosive fashion at around 42 °C, as demonstrated in a molecular-beam mass spectrometry study. The precursor is also shown to serve as a PN transfer reagent in the synthesis of an Fe–NP coordination complex, through ligand exchange with its Fe–N2 counterpart. The terminal N-bonded complex was found to be energetically preferred, compared to its P-bonded linkage isomer, owing to a significant covalent Fe–pnictogen bond character and an associated less unfavourable Pauli repulsion in the metal–ligand interaction.