Journal article

Authors list: Qian, WY; Wende, RC; Schreiner, PR; Mardyukov, A

Publication year: 2023

Journal: Angewandte Chemie International Edition

Volume number: 62

Issue number: 23

ISSN: 1433-7851

eISSN: 1521-3773

Open access status: Hybrid

DOI Link: https://doi.org/10.1002/anie.202300761

Publisher: Wiley

Abstract: 
The interstellar candidate phosphorus mononitride PN, a metastable species, was generated through high-vacuum flash pyrolysis of (o-phenyldioxyl)phosphinoazide in cryogenic matrices. Although the PN stretching band was not directly detected because of its low infrared intensity and possible overlaps with other strong bands, o-benzoquinone, carbon monoxide, and cyclopentadienone as additional fragmentation products were clearly identified. Moreover, an elusive o-benzoquinone-PN complex formed when (o-phenyldioxyl)phosphinoazide was exposed to UV irradiation at lambda=254 nm. Its recombination to (o-phenyldioxyl)-lambda(5)-phosphinonitrile was observed upon irradiation with the light at lambda=523 nm, which demonstrates for the first time the reactivity of PN towards an organic molecule. Energy profile computations at the B3LYP/def2-TZVP density functional theory level reveal a concerted mechanism. To provide further evidence, UV/Vis spectra of the precursor and the irradiation products were recorded and agree well with time-dependent DFT computations.

Harvard Citation style: Qian, W., Wende, R., Schreiner, P. and Mardyukov, A. (2023) Selective Preparation of Phosphorus Mononitride (P equivalent to N) from Phosphinoazide and Reversible Oxidation to Phosphinonitrene, Angewandte Chemie International Edition, 62(23), Article e202300761. https://doi.org/10.1002/anie.202300761

APA Citation style: Qian, W., Wende, R., Schreiner, P., & Mardyukov, A. (2023). Selective Preparation of Phosphorus Mononitride (P equivalent to N) from Phosphinoazide and Reversible Oxidation to Phosphinonitrene. Angewandte Chemie International Edition. 62(23), Article e202300761. https://doi.org/10.1002/anie.202300761