New {RuNO} Polyoxometalate [PW₁₁O₃₉Ru^II(NO)]^4-: Synthesis and Reactivity

Abstract

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Easy Ligand Activation in the Coordination Sphere of Ru inside the [PW11O39]7– Backbone

“…The oxidation process at 0.92 V corresponds to Ru(II)/Ru(III) couple. It was previously found that a similar Ru-NO complex reversibly oxidizes at 1.29 V (vs. Ag/AgCl) [20]. Two redox processes at −0.33 and −1.64 V should correspond to the reduction of W(VI) in the {PW11} framework, as is well documented.…”

“…Catalytic activities of [PW11O39Ru III (H2O)] 4− , [PW11O39Ru II (DMSO)] 5− (DMSO: dimethyl sulfoxide), [SiW11O39Ru III (H2O)] 5− , [SiW11O39Ru III (DMSO)] 5− , and [GeW11O39Ru III (H2O)] 5− in oxidation of olefins [3][4][5], water [6][7][8], DMSO [9,10], and alcohols [11,12]; reduction of DMSO [10] and carbon dioxide [13]; and oxidative C-C bond formation [14] have been reported. The H2O ligand attached to Ru is exchangeable with other organic and inorganic donor molecules to form Ru-pyridine [10,15,16], Ru-pyrazine [12], Ru-DMSO [10,17,18], Ru-NO [19][20][21], Ru-Cl [22], Ru-CO [23][24][25], Ru-olefin [10], and Ru-O-Ru derivatives [26,27].…”

“…In 2013 we reported incorporation of a {Ru(NO)} 3+ group into a Keggin type POM, [PW11O39] 7− , and versatile reactivity of the coordinate NO ligand [20,21]. Easily available [Ru(NO)Cl5] 2− offers serious advantages as Ru source for preparation of Ru-substituted Keggin-type heteropolytungstates due to the redox stability of the {Ru(NO)} 3+ unit, hydrolytic inertness, and consequent lack of uncontrollable hydrolytic oligomerization, though the inertness of coordinated Cl ligands in this lowspin d 6 -Ru(II) complex requires drastic reaction conditions.…”

Gas‐Phase Fragmentation Reactions of Keggin‐Type {PW11O39M} (M = Rh, Ir, and Ru) Polyoxometalates as Fingerprints of the Ligands Attached at the Noble Metal Site

“…CID techniques in the investigation of the Lindqvist [Mo 6 O 19 ] 2– and [W 6 O 19 ] 2– dianions17 proved to be a convenient source of smaller gas‐phase ions for subsequent gas‐phase reactivity studies towards methanol18 and shed light on the preferred nucleation steps leading to the Lindqvist dianions 19. We recently reported that the fragmentation reactions of some Keggin‐type {PW 11 O 39 Ru} POMs under CID conditions allowed the identification of the chemical environment of the noble metal site through the release of the specific neutral ligand (H 2 O, NO, N 2 or NH 3 ) attached at the Ru site 12a. Herein, we explore the possibility to extend this approach to other Keggin‐type {PW 11 O 39 M} homologues with Rh and Ir (see Scheme ) and different countercations to validate whether fragmentation reactions under CID conditions may be used as fingerprints of the chemical environment around the noble metal site.…”

Preparation, characterization and catalytic activity studies of organoruthenium‐supported polyoxotungstates on SBA‐15

“…Amongst POMs, ruthenium‐containing POMs (Ru‐POMs) have attracted increasing attention in recent years due to their attractive catalytic properties and long‐promised potential as catalysts . On the one hand, Ru‐POMs exhibit excellent catalytic activities in catalytic oxidation processes of various organic substrates, e.g.…”