Staudinger Reactivity and Click Chemistry of Anthracene (A)-Based Azidophosphine N₃PA

11-Azido-9,10-dihydro-9,10-phosphanoanthracene (N₃PA) has been demonstrated recently as a transfer reagent for molecular phosphorus mononitride (PN) because it easily dissociates at room temperature into dinitrogen (N₂), PN, and anthracene (A). Here we report further reactivity studies of the N₃PA molecule including strain-promoted 1,3-dipolar cycloaddition with cyclooctyne and Staudinger-type reactivity. Calculations at the DLPNO-CCSD(T)/cc-pVTZ//PBE0-D3(BJ)/cc-pVTZ level of theory indicate that the click reaction is faster than the dissociation of N₃PA. The Staudinger-type reactivity enabled transfer of the NPA fragment to a base-stabilized silylene. The previously reported intermediate of vanadium trisanilide with an NPA ligand could be isolated in 61% yield and structurally characterized in a single-crystal X-ray diffraction experiment. In line with the previously reported phosphinidene reactivity of the transient vanadium phosphorus mononitride complex, thermolysis or irradiation of the complex leads to A elimination and formation of the corresponding vanadium PN dimer or trimer, respectively.