The elusive cyclotriphosphazene molecule and its Dewar benzene-type valence isomer (P<sub>3</sub>N<sub>3</sub>).
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 32832667.
- Also identified by DOI 10.1126/sciadv.aba6934 and PMC identifier 7439403.
- Licence recorded as CC BY-NC.
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Abstract
Although the chemistry of phosphorus and nitrogen has fascinated chemists for more than 350 years, the Hückel aromatic cyclotriphosphazene (P<sub>3</sub>N<sub>3</sub>, <b>2</b>) molecule-a key molecular building block in phosphorus chemistry-has remained elusive. Here, we report a facile, versatile pathway producing cyclotriphosphazene and its Dewar benzene-type isomer (P<sub>3</sub>N<sub>3</sub>, <b>5</b>) in ammonia-phosphine ices at 5 K exposed to ionizing radiation. Both isomers were detected in the gas phase upon sublimation via photoionization reflectron time-of-flight mass spectrometry and discriminated via isomer-selective photochemistry. Our findings provide a fundamental framework to explore the preparation of inorganic, isovalent species of benzene (C<sub>6</sub>H<sub>6</sub>) by formally replacing the C─H moieties alternatingly through phosphorus and nitrogen atoms, thus advancing our perception of the chemical bonding of phosphorus systems.