Hydrothermal Synthesis and Structural Characterization of the High‐Valent Ruthenium‐Containing Polyoxoanion [{PW₁₁O₃₉}₂{(HO)RuIV–O–RuIV(OH)}]¹⁰–

The high‐valent ruthenium‐containing [{PW 11 O 39 } 2 {(HO)Ru IV –O–Ru IV (OH)}] 10– anion ( 1 ) has been synthesized by hydrothermal reaction and characterized by X‐ray diffraction, IR, multinuclear ( 31 P and 183 W) NMR spectroscopy andelectrochemistry. Single‐crystal analysis was carried outon Rb 10 [{PW 11 O 39 } 2 {(HO)Ru IV –O–Ru IV (OH)}] · 21H 2 O, which crystallizes in the monoclinic system, space group P 2 1 / n , with a = 11.1912(14), b = 21.9257(12), c = 38.7310(96) Å, β = 94.682(19)°, V = 9472(3) Å 3 , Z = 4. Polyanion 1 consists of two lacunary [α‐PW 11 O 39 ] 7– anions connected by a linear {(HO)Ru–O–Ru(OH)} 4+ unit. Each ruthenium ion achieves six‐coordination through interaction with two terminal oxo ligands from the lacuna of each [PW 11 O 39 ] 7– anion.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)