Phosphine and carbene azido-cations: [(L)N3]+ and [(L)2N3]+

The cationic N-3-species [(p-HC6F4)(3)PN3](+) (1) featuring a perfluoro-arene phosphonium group serves as a N-3(+)-source in stoichiometric reactions with several Lewis bases (L) allowing for the stepwise formation of [(L)N-3](+) and [(L)(2)N-3](+) cations (L = phosphine, carbene) with liberation of (p-HC6F4)(3)P. X-Ray diffraction analysis and computational studies provide insight into the bonding in these remarkably stable azidocations.