Triphenylpnictogens EPh3 (E = N, P, As, Sb, Bi) are able to displace the perfluorinated Cp* ligand in [Rh(COD)(C5(CF3)5)] (COD = 1,5-cyclooctadiene) in up to quantitative yield. The resulting ionic products contain [C5(CF3)5]− as uncoordinated counter anion. The cations feature [Rh(COD)]+ fragments, coordinated by one (N, Bi), two (P, As) or three (Sb) triphenylpnictogen moieties. Whereas coordination via the pnictogen is observed for P, As and Sb, π-coordination of the aryl rings is observed for N and Bi.
