Discrete Platinum(II/IV)–Arsenito Clusters with Pt–As and Pt–O Bonding: [Pt IV (As 3 O 6 ) 2 ] 2– , [Pt 4 II (H 2 AsO 3 ) 6 (HAsO 3 ) 2 ] 2– , and [Pt 2 II As 6 W 4 O 28 ] 10

The first two discrete, fully inorganic platinum(II/IV)-arsenito clusters, [fac-PtIV(As3O6)2]2- (PtAs6) and [Pt4II(H2AsO3)6(HAsO3)2]2- (Pt4As8), as well as the platinum(II)-arsenito heteropolytungstate [Pt2IIAs6W4O28]10- (Pt2As6W4), have been synthesized in aqueous media using simple one-pot reaction conditions. In PtAs6, a PtIV ion is coordinated to two cyclic, tridentate As3O6 units via oxo-donation (PtIV-O ∼ 2.02 Å). In Pt4As8, each PtII ion is coordinated to four AsO3 ligands via two oxygens and two AsIII atoms in a square-planar fashion (PtII-AsIII 2.31 Å, PtII-O 2.07 Å), resulting in an open cage-like structure, which forms a strong tetrameric assembly in the solid state mediated by two K+ counterions. In Pt2As6W4, each PtII ion is coordinated by the As atoms of three AsO3 ligands (PtII-AsIII 2.38 Å) and an oxo group (PtII-O 2.07 Å) in addition to bridging two tungsten ions, and this polyanion was characterized in solution by 195Pt NMR.