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

The cationic N3-species [(p-HC6F4)3PN3]+ (1) featuring a perfluoro-arene phosphonium group serves as a N3+-source in stoichiometric reactions with several Lewis bases (L) allowing for the stepwise formation of [(L)N3]+ and [(L)2N3]+ cations (L = phosphine, carbene) with liberation of (p-HC6F4)3P. X-Ray diffraction analysis and computational studies provide insight into the bonding in these remarkably stable azido-cations.