Selective Preparation of Phosphorus Mononitride (P≡N) from Phosphinoazide and Reversible Oxidation to Phosphinonitrene

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...

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Published inAngewandte Chemie International Edition Vol. 62; no. 23; pp. e202300761 - n/a
Main Authors Qian, Weiyu, Wende, Raffael C., Schreiner, Peter R., Mardyukov, Artur
Format Journal Article
LanguageEnglish
Published Germany Wiley Subscription Services, Inc 05.06.2023
EditionInternational ed. in English
Subjects
Benzoquinone
Carbon cycle
Carbon monoxide
Density functional theory
Irradiation
Matrix Isolation
Nitrenes
Organic chemistry
Oxidation
Phosphorus
Phosphorus Mononitride
Photochemistry
Pyrolysis
Recombination
Time dependence
Ultraviolet radiation
Nitrenes
Phosphorus Mononitride
Matrix Isolation
Photochemistry
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Summary: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. An o‐benzoquinone complex bearing a P≡N unit displays reversible covalent‐bond formation when exposed to green light in cryogenic matrices. This is the first demonstration of the reactivity of phosphorus mononitride towards an organic molecule.
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ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202300761