Carbene-stabilized phosphorus(III)-centered cations [LPX(2)](+) and [L(2)PX](2+) (L = NHC; X = Cl, CN, N(3)).

A versatile, high-yielding synthesis of NHC-stabilized [PCl(2)](+) and [PCl](2+) phosphorus synthons has been achieved by using an "onio-substituent transfer" reagent. Subsequent functionalization yields access to cationic cyano- and azido-substituted derivatives which represent first examples of a displacement reaction on NHC-stabilized phosphorus(III)-centered cations. The new salts have been fully characterized by NMR spectroscopy and X-ray crystallography.