Various Oxygen-Centered Phosphanegold(I) Cluster Cations Formed by Polyoxometalate (POM)-Mediated Clusterization: Effects of POMs and Phosphanes

Novel phosphanegold(I) cluster cations combined with polyoxometalate (POM) anions, i.e., intercluster compounds, [(Au{P(m-FPh)3})4(μ4-O)]2[{(Au{P(m-FPh)3})2 (μ-OH)}2][α-PMo12O40]2·EtOH (1), [(Au{P(m-FPh)3})4(μ4-O)]2[α-SiMo12O40]·4H2O (2), [(Au{P(m-MePh)3})4(μ4-O)]2[α-SiM12O40] (M = W (3), Mo (4)) and [{(Au {P(p-MePh)3})4(μ4-O)}{(Au{P(p-MePh)3})3(μ3-O)}][α-PW12O40] (5) were synthesized by POM-mediated clusterization, and unequivocally characterized by elemental analysis, TG/DTA, FT-IR, X-ray crystallography, solid-state CPMAS 31P NMR and solution (1H, 31P{1H}) NMR. Formation of the these gold(I) cluster cations was strongly dependent upon the charge density and acidity of the POMs, and the substituents and substituted positions on the aryl group of triarylphosphane ligands. These gold(I) cluster cations contained various bridged-oxygen atoms such as μ4-O, μ3-O and μ-OH groups.