Substitution Lability of the Perfluorinated Cp* Ligand in [Rh(COD)(C5(CF3)5)] Towards Triphenylpnictogens EPh3 (E=N, P, As, Sb, Bi).

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.

Synthesis and structural characterization of stable coinage metal (Cu, Ag, Au) cyclopentadienyl complexes.

The electron withdrawing and oxidatively stable perfluorinated Cp* ligand [C5(CF3)5]- allowed for the isolation of rare and unusually stable coinage metal complexes [M(C5(CF3)5)(PtBu3)] (M = Cu, Ag, Au), representing the first complete and structurally comparable series of group 11 Cp coordination compounds. Full characterization and structure analysis revealed distinct and partly unknown coordination motifs with hapticities ranging from η1, η3/η1 and η3/η2 for gold, silver and copper, respectively. Quantum-chemical studies using DFT methods confirm these findings and connect them to the unique electronic structure of the given ligand system.