Discovery of Polythioplatinate(II) [Pt₃S₂(SO₃)₆]^10- and Study of Its Solution and Catalytic Properties

We have discovered the first polythioplatinate(II), [Pt^II₃S₂(SO₃)₆]^10- (1), which was synthesized in aqueous basic medium (pH 11) by hydrothermal heating at 150 °C. Polyanion 1 comprises a discrete, triangular assembly of three Pt²⁺ ions linked by two μ₃-sulfido ligands, and their square-planar coordination geometry is completed by two terminal S-bound sulfito ligands. Polyanion 1 was isolated as a hydrated sodium salt, Na₁₀[Pt^II₃(μ₃-S)₂(SO₃)₆]·22H₂O (Na-1), which was characterized in the solid state by single-crystal X-ray diffraction, Fourier-transform infrared spectroscopy, thermogravimetric analysis, X-ray photoelectron spectra, and elemental analysis, in solution by ¹⁹⁵Pt NMR and atomic absorption spectroscopy, and in the gas phase by electrospray ionization mass spectrometry. Density functional theory calculations were performed, and the ¹⁹⁵Pt NMR chemical shifts of 1 were computed theoretically and shown to match well with the experimental data. Furthermore, the discrete title polyanion 1 was immobilized on mesoporous SBA-15 support and used as a precatalyst for the hydrogenation of o-xylene.