Because PN is not stable under ambient conditions, we needed a molecular precursor in order to probe its reaction chemistry. Our design for a PN source involved sandwiching it between two neutral leaving groups, N2 and anthracene, A. The required azidophosphine N3PA was prepared from ClPA and sodium azide in the cold, using lithium chloride as a phase transfer catalyst. As expected, the azidophosphine N3PA explodes upon heating above 40 °C. The fragmentation reaction was explored using molecular beam mass spectroscopy, and PN was detected among the earliest burst of fragments, together with A and N2. In solution, the fragmentation reaction follows a first-order kinetic profile with a half-life of roughly half an hour. Reaction of the PN molecular precursor with an iron complex led to the isolation and crystallization of a complex with PN as a terminal N-bonded ligand. The spectroscopic and other properties of the iron PN complex will be described in detail.

Taming phosphorus mononitride

ACS Spring 2022

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