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

Abstract

The high‐valent ruthenium‐containing [{PW11O39}2{(HO)RuIV–O–RuIV(OH)}]10– anion (1) has been synthesized by hydrothermal reaction and characterized by X‐ray diffraction, IR, multinuclear (31P and 183W) NMR spectroscopy andelectrochemistry. Single‐crystal analysis was carried outon Rb10[{PW11O39}2{(HO)RuIV–O–RuIV(OH)}]·21H2O, which crystallizes in the monoclinic system, space group P21/n, with a = 11.1912(14), b = 21.9257(12), c = 38.7310(96) Å, β = 94.682(19)°, V = 9472(3) Å3, Z = 4. Polyanion 1 consists of two lacunary [α‐PW11O39]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 [PW11O39]7– anion.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

A Crown‐Shaped Ru‐Substituted Arsenotungstate for Selective Oxidation of Sulfides with Hydrogen Peroxide

“…Through unremitting efforts, we have now succeeded in preparing a new crown-shaped Ru-substituted arsenotungstate [H 2 N(CH 3 ) 2 ] 14 [As 4 W 40 O 140 {Ru 2 (CH 3 COO)} 2 ]·22 H 2 O( 1)b yr eaction of Na 2 WO 4 ·2H 2 O, NaAsO 2 ,a nd RuCl 3 in am olarr atio of 7.7:1.1:1.0 in sodium acetate buffers olution( 0.5 mol L À1 , pH 4.3) in the presence of dimethylamine hydrochloride (Scheme 1). As ar esult,i tc an be quite difficult to identify appropriate reactionc onditions allowing access to novel RSKPs.…”

A new synthetic route towards a Ru(III) substituted heteropolytungstate anion

“…During our investigation of Ru(III) (or higher oxidation state) POM derivatives [7,8], the report of [Ru(dmf) 6 ](CF 3 SO 3 ) 3 and [Ru-(dmf) 6 ](CF 3 SO 3 ) 2 (dmf = dimethylformamide) [9] species caught our attention: (i) [Ru(dmf) 6 ] 2+ is more readily accessible than [Ru II (OH 2 ) 6 ] 2+ and its reactivity towards lacunary POMs followed by O 2 oxidation, according to Pope's procedure, is thus worth studying; (ii) providing some activation, [Ru(dmf) 6 ] 3+ could also prove to be a convenient precursor. We thus decided to study its reactivity under microwave irradiation, a strategy first reported by Bonchio for the synthesis of [PW 11 which was first isolated as a caesium salt after addition of CsCl [11].…”

“…This procedure relies on the greater lability of Ru(II) but is limited by the preparation of [Ru II (OH 2 ) 6 ] 2+ , which is not trivial. As an alternative, hydrothermal syntheses of Ru(III) or Ru(IV) derivative of POMs have been reported: mono-ruthenium substituted Keggin-type silicotungstates and l-oxo bridged dimers have been thus synthesised from [Ru(acac) 3 ] [6] or [Ru 2 (OAc) 4 ]Cl [7].…”

A Novel Ruthenium-Decorating Polyoxomolybdate Cs3Na6H[MoVI14RuIV2O50(OH)2]·24H2O: An Active Heterogeneous Oxidation Catalyst for Alcohols

“…Among them, the wholly inorganic Ru-containing POMs represent an important subclass, which had been studied previously but with only a few structures reported as compared to those with inorganic-organic hybrid Ru-containing POMs. Up until now, the majority of investigations in this area of research have been dominated by the preparations and characterizations of Ru-substituted or -sandwiched lacunary Keggin/Dawson-type heteropolytungstates [2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43], such as mono-Ru substituted polyanions [XW 11 O 39 Ru III (H 2 O)] n− (X = Si, Ge, P) [2,3,4,5,20,21,22,23,24,25] and [P 2 W 17 O 61 Ru III (H 2 O)] 5− [26,27,28], di-Ru-sandwiched/substituted polyanions {O[Ru IV (X)P 2 W 17 O 61 ] 2 } 16− (X = OH, Cl) [27], {[(XZnRu 2 III (OH)(H 2 O)](ZnW 9 O 34 ) 2 } n− (X = W, Zn) [29,30,…”