Selective Preparation of Phosphorus Mononitride (P≡N) from Phosphinoazide and Reversible Oxidation to Phosphinonitrene |
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Authors: | Weiyu Qian Dr Raffael C Wende Prof Dr Peter R Schreiner Dr Artur Mardyukov |
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Institution: | Institute of Organic Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, 35392 Giessen, Germany |
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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 λ=254 nm. Its recombination to (o-phenyldioxyl)-λ5-phosphinonitrile was observed upon irradiation with the light at λ=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. |
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Keywords: | Matrix Isolation Nitrenes Phosphorus Mononitride Photochemistry |
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