Phosphine and carbene azido-cations: [(L)N 3 ] + and [(L) 2 N 3 ]

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