P–P Condensation and P/N–P/P bond metathesis: Facile Synthesis of Cationic Tri‐ and Tetraphosphanes

[LC (R) P((PhP)2 C2 H4 )][OTf] (4 a,b[OTf]) and [LC (iPr) P(PPh2 )2 ][OTf] (5 b[OTf]) were prepared from the reaction of imidazoliumyl-substituted dipyrazolylphosphane triflate salts [LC (R) P(pyr)2 ][OTf] (3 a,b[OTf]; a: R=Me, b=iPr; LC (R) =1,3-dialkyl-4,5-dimethylimidazol-2-yl; pyr=3,5-dimethylpyrazol-1-yl) with the secondary phosphanes PhP(H)C2 H4 P(H)Ph) and Ph2 PH. A stepwise double P-N/P-P bond metathesis to catena-tetraphosphane-2,3-diium triflate salt [(Ph2 P)2 (LC (Me) P)2 ][OTf]2 (7 a[OTf]2 ) is observed when reacting 3 a[OTf] with diphosphane P2 Ph4 . The coordination ability of 5 b[OTf] was probed with selected coinage metal salts [Cu(CH3 CN)4 ]OTf, AgOTf and AuCl(tht) (tht=tetrahydrothiophene). For AuCl(tht), the helical complex [{(Ph2 PPLC (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(CH3 CN)3 ][OTf]2 (M=Cu, Ag) (10[OTf]2 , 11[OTf]2 ).