The reaction of the bis(imidazoliumyl)-substituted P I cation [(2-Im Dipp )P(4-Im Dipp )] + (10 + )(2-Im = imidazolium-2-yl;4 -Im = imidazolium-4-yl;D ipp = 2,6-di-isopropylphenyl) with trifluoromethanesulfonic acid (HOTf) or methyl trifluoromethylsulfonate (MeOTf) yields the corresponding protonated [(2-Im Dipp )PH(4-Im Dipp )] 2+ (11 2+ )a nd methylated [(2-Im Dipp )PMe(4-Im Dipp )] 2+ (12 2+ )d ications, respectively.E PR/UV/Vis-NIR spectroelectrochemical investigation of the low-coordinated P I cation 10 + predicted astable and "bottleable" P-centered radical dication [(2-Im Dipp )P(4-Im Dipp )] 2+ C (13 2+ C). The reaction of 10 + with the nitrosyl salt NO[OTf] yields the persistent phosphanyl radical dication 13 2+ C as triflate salt in crystalline form. Quantum chemical investigation revealed an exceptional high spin density at the Patom.Among several bonding motifs possible for charged and uncharged P 1 -centered radicals,p hosphanyl radicals are particularly intriguing. [1] Such radicals feature at wo-coordinate Patom in the + II oxidation state in combination with either C-(I) or N-based (II)-or ac ombination of both (III)-substituents L C or L N (Scheme 1). Especially lowcoordinate P-radical species require stabilization by either bulky substituents (kinetic stabilization), and/or spin delocalization (thermodynamic stabilization). [2] However, only af ew examples are known that are stable enough to be isolated in the solid state.Representative examples of isolated and structurally characterized neutral (1C-5C), [3][4][5][6] anionic (6 À C), [7] and cationic (7 + C, 8 + C) [8,9] derivatives are depicted in Scheme 1. Thestability of the radical cations is also explained by the positive charge leading to electrostatic repulsive effects.S urprisingly,a nd to the best of our knowledge,n o example of ap hosphanyl radical dication has been reported so far,although with the isolation of radical cations of type 7 + C and 8 + C those species should be feasible.T hus,adicationic radical species might be accessible by af ormal exchange of the L N substituent in cations of type 7 + C or 8 + C by an imidazoliumyl substituent. Recently,w er eported on the high-yielding synthesis of the cationic phosphanide 10 + , bearing two lone pairs of electrons at the Patom, which we obtained from the reduction of dication 9 2+ (Scheme 2). [10] Cation 10 + is supposed to react with electrophiles such as trifluoromethanesulfonic acid (HOTf) or methyl trifluoromethylsulfonate (MeOTf) to give the respective protonated (11 2+ )a nd methylated dications (12 2+ )a st riflate salts, respectively (Scheme 2). Theu nique combination of the Cbonded N-heterocyclic substituents (L C )o nt he two-coordinate phosphorus atom in cation 10 + makes it an excellent substrate for the synthesis of the hitherto unknown phosphanyl radical dication 13 2+ C (Scheme 2).Reacting 10 + with HOTf or MeOTf in CH 2 Cl 2 gives the expected dications 11 2+ (88 %) and 12 2+ (83 %) as triflate salts in very good yield (Scheme 2). [11] Both compounds are obtained as ...