P−P Condensation and P−N/P−P Bond Metathesis: Facile Synthesis of Cationic Tri‐ and Tetraphosphanes

[L(C) (R)P((PhP)(2)C(2)H(4))][OTf] (4 a,b[OTf]) and [L(C) (iPr)P(PPh(2))(2)][OTf] (5 b[OTf]) were prepared from the reaction of imidazoliumyl‐substituted dipyrazolylphosphane triflate salts [L(C) (R)P(pyr)(2)][OTf] (3 a,b[OTf]; a: R=Me, b=iPr; L(C) (R)=1,3‐dialkyl‐4,5‐dimethylimidazol‐2‐yl; pyr=3,5‐dimethylpyrazol‐1‐yl) with the secondary phosphanes PhP(H)C(2)H(4)P(H)Ph) and Ph(2)PH. A stepwise double P−N/P−P bond metathesis to catena‐tetraphosphane‐2,3‐diium triflate salt [(Ph(2)P)(2)(L(C) (Me)P)(2)][OTf](2) (7 a[OTf](2)) is observed when reacting 3 a[OTf] with diphosphane P(2)Ph(4). The coordination ability of 5 b[OTf] was probed with selected coinage metal salts [Cu(CH(3)CN)(4)]OTf, AgOTf and AuCl(tht) (tht=tetrahydrothiophene). For AuCl(tht), the helical complex [{(Ph(2)PPL(C) (iPr))Au}(4)][OTf](4) (9[OTf](4)) was unexpectedly formed as a result of a chloride‐induced P−P bond cleavage. The weakly coordinating triflate anion enables the formation of the expected copper(I) and silver(I) complexes [(5 b)M(CH(3)CN)(3)][OTf](2) (M=Cu, Ag) (10[OTf](2), 11[OTf](2)).