Preparation of tetrabutylammonium salt of a mono-Ru(III)-substituted α-Keggin-type silicotungstate with a 4,4'-bipyridine ligand and its electrochemical behaviour in organic solvents.

The tetrabutylammonium (TBA) salt of a mono-ruthenium(III)-substituted α-Keggin-type silicotungstate with a 4,4'-bipyridine (bipy) ligand, TBA5[α-SiW11O39Ru(III)(bipy)] (1), which is soluble in various organic solvents, was prepared by a cation exchange reaction of Cs5[α-SiW11O39Ru(III)(bipy)] with tetrabutylammonium bromide. Compound 1 was characterised using IR, (1)H-NMR, elemental analysis, single crystal X-ray analysis, X-ray absorption near-edge structure (XANES) analysis (Ru L3-edge), electron spin resonance (ESR), cyclic voltammetry (CV) and UV-Vis. Single crystal X-ray analysis of 1 revealed that the Ru(III) unit was incorporated into the α-Keggin-type silicotungstate framework and coordinated by a bipy molecule through a Ru-N bond.

Stabilization of high-valence ruthenium with silicotungstate ligands: preparation, structural characterization, and redox studies of ruthenium(III)-substituted α-Keggin-type silicotungstates with pyridine ligands, [SiW11O39Ru(III)(Py)]5-.

Ruthenium(III)-substituted α-Keggin-type silicotungstates with pyridine-based ligands, [SiW(11)O(39)Ru(III)(Py)](5-), (Py: pyridine (1), 4-pyridine-carboxylic acid (2), 4,4'-bipyridine (3), 4-pyridine-acetamide (4), and 4-pyridine-methanol (5)) were prepared by reacting [SiW(11)O(39)Ru(III)(H(2)O)](5-) with the pyridine derivatives in water at 80 °C and then isolated as their hydrated cesium salts. These compounds were characterized using cyclic voltammetry (CV), UV/Vis, IR, and (1)H NMR spectroscopy, elemental analysis, titration, and X-ray absorption near-edge structure (XANES) analysis (Ru K-edge and L(3)-edge). Single-crystal X-ray analysis of compounds 2, 3, and 4 revealed that Ru(III) was incorporated in the α-Keggin framework and was coordinated by pyridine derivatives through a Ru-N bond.