Reactivity of a Stable Phosphinonitrene towards Small Molecules

The room‐temperature stable phosphinonitrene 1 undergoes a thermal rearrangement into heterocycle 2 through a process involving a nitrene insertion into a CH bond. In the presence of acetonitrile, a nitrene–acetonitrile adduct has been isolated; then it first rearranges into a ketenimine and subsequently into a rare example of diazaphosphete. Compound 1 also splits water, carbon dioxide, carbon disulfide, and elemental sulfur, although it reacts with white phosphorus, leading to a P₅N cluster formally resulting from the insertion of the PN moiety into a P?P edge of the P₄ tetrahedron.