Synthesis and Characterization of Intercluster Compounds Consisting of Various Gold Clusters and Differently Charged Keggin Anions

The crystal structures of five intercluster compounds consisting of gold clusters and Keggin anions have been determined by single‐crystal x‐ray diffraction: [Au₉(PPh₃)₈][PMo₁₂O₄₀] (P4/n, Z = 2, a = 24.0195(13), c = 13.6818(10) Å), [Au₉(PPh₃)₈][HSiMo₁₂O₄₀] (P4/n, Z = 2, a = 24.270(3), c = 13.752(2) Å), [Au₉(PPh₃)₈][H₃CoW₁₂O₄₀] (P4/n, Z = 2, a = 24.4776(16), c = 13.7759(13) Å), [Au₈(PPh₃)₈]₂[SiMo₁₂O₄₀] (Pbca, Z = 4, a = 36.269(4), b = 24.488(3), c = 38.612(4) Å) and (nBu₄N)[Au₉(Ptol₃)₈][SiMo₁₂O₄₀] (Cc, Z = 4, a = 24.832(5), b = 24.955(5), c = 40.096(8) Å, β = 106.744(3)°). In these compounds, the charges of the building blocks were varied. Altering the charge on the Keggin anion in combination with the [Au₉(PPh₃)₈]³⁺ cluster gave rise to isostructural compounds as the charge is compensated by protonation of the polyoxometalate anion. Varying the charge or the ligand type of the gold cluster led to compounds with a completely different packing principle.