An unknown component of a selective and mild oxidant: structure and oxidative ability of a double salt-type complex having κ<sup>1</sup>O-coordinated permanganate anions and three- and four-fold coordinated silver cations

Kovács, Gréta Bettina; May, Nóra V.; Bombicz, Petra; Klébert, Szilvia; Németh, Péter; Menyhárd, Alfréd; Novodárszki, Gyula; Petruševski, Vladimir M.; Franguelli, Fernanda Paiva; Magyari, József; Béres, Kende Attila; Szilágyi, Imre Miklós; Kótai, László

doi:10.1039/c9ra03230d

Cited by 24 publications

(61 citation statements)

References 50 publications

(25 reference statements)

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“…Since in our compounds there are strongly reducing cations and oxidizing anions, one can expect a thermally induced redox reaction between them. The occurrence of such kind of redox reactions within one compound having oxidizing and reducing components is well documented in the literature [11][12][13][14][15][16][17]. Since in inert atmosphere the decomposition steps are endothermic, one can conclude that the energy required for elimination of water and dimethylamine as well as the disruption of the lattice exceeds the exothermicity of the redox interaction.…”

Section: Resultsmentioning

confidence: 94%

Thermal analysis of solvatomorphic decakis (dimethylammonium) dihydrogendodecatungstate hydrates

Trif

Franguelli

Lendvay

et al. 2021

J Therm Anal Calorim

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This study aims to describe the thermal decomposition of two solvatomorphs of decakis(dimethylammonium) dihydrogendodecatungstate ((Me2NH2)10H2W12O42·10H2O and 11 H2O) under inert and oxidizing atmospheres. Thermal studies have been done by TG-MS, TG-DSC-MS, XRD and IR methods in both synthetic air and helium atmospheres. The general characteristics of thermal decomposition are similar for both solvatomorphs. Minor differences could be observed in the resolution and shifting of the decomposition peak temperatures depending on the heating rate or atmosphere used. The first step of decomposition is endothermic in both atmospheres and involves 2 and 5 water molecule elimination with ~ 150 and ~ 120 °C peak temperatures for the decahydrate and undecahydrate, respectively. The elimination of further water and dimethylamine was observed with increasing the temperature, as well as the disruption of the lattice of compounds. Until 300 °C, these processes are endothermic in both atmospheres, and the further decomposition processes at higher temperatures are left endothermic in helium, but become exothermic in synthetic air atmosphere. In helium atmosphere, above 350 °C, a solid-phase quasi-intramolecular redox reaction takes place when the dimethylamine degradation products react with the W=O bonds with formation of oxidative coupling products of the organic fragments and reduced tungsten oxide with WO~2.93 composition. In synthetic air, above 350 °C, burning of organic fragments takes place, there are no oxidative coupling products and reduced tungsten oxide formation, and the end product of decomposition is monoclinic WO3.

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Section: Resultsmentioning

confidence: 94%

Thermal analysis of solvatomorphic decakis (dimethylammonium) dihydrogendodecatungstate hydrates

Trif

Franguelli

Lendvay

et al. 2021

J Therm Anal Calorim

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“…Comparison of the Ag…O-ClO 3 distance in compound 1 with the Ag…O-MnO 3 distance in 1-MnO 4 (2.601 Å ) indicates that the coordination strength of the perchlorate to the silver ion is weaker than that of the permanganate. The deviation of the N-Ag-N angle from the ideal 180°is somewhat larger in the perchlorate (6.26°) [15] than in the permanganate (6.15°) [17].…”

Section: Synthesis and Structural Featuresmentioning

confidence: 86%

“…1). It is isomorphous with the permanganate analog [17]. The unit cell volume of 1 is 0.85% larger than that of compound 1-MnO 4 ; their cell similarity index (p) [18] is 0.00044.…”

Section: Synthesis and Structural Featuresmentioning

confidence: 99%

Thermal and spectroscopic studies on a double-salt-type pyridine–silver perchlorate complex having κ1-O coordinated perchlorate ions

Holló

Petruševski

Kovács

et al. 2019

J Therm Anal Calorim

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A simple synthetic method was developed to prepare 4[Agpy 2 ClO 4 ]Á[Agpy 4 ]ClO 4 in a low-temperature decomposition process of [Agpy 4 ]ClO 4 . A detailed IR, Raman and far-IR study including factor group analysis has been performed, and the assignation of bands is given. The compound decomposes quickly with a multistep ligand loss process with the formation of [Agpy 2 ]ClO 4 and AgClO 4 intermediates and AgCl as an end product around * 85, * 350 and 450°C, respectively. During the first decomposition step, a small fraction of the ligands is lost in a redox reaction: perchlorate oxidizes the pyridine, forming carbon, carbon dioxide, water and NO, while it itself is reduced into AgCl. In the next step, when AgClO 4 forms after complete ligand loss and reacts with the carbon formed in the degradation of pyridine at lower temperatures and produces NO, CO 2 and H 2 O. This reaction becomes possible because the AgCl formed in the redox reactions makes a eutectic melt with AgClO 4 in situ, which is a favorable medium for the carbon oxidation reaction. AgCl is known to reduce the temperature of decomposition of AgClO 4 , in which process forms AgCl as well as O 2 and so is an autocatalytic process. The loss and degradation of pyridine ligand are endothermic; the redox reactions including carbon oxidation and AgClO 4 decomposition into AgCl and O 2 are exothermic. The amount of absorbed/evolved heats corresponding to these processes was determined by DSC both under N 2 and O 2 atmospheres. Keywords Pyridine-silver complexes Á Perchlorates Á Quasi-intramolecular solid-phase redox reaction Á Evolved gas analysis Á DSC Electronic supplementary material The online version of this article (

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“…The silver content was removed and analyzed as AgCl (with HCl addition), whereas the manganese(II) content was determined gravimetrically as oxinate. 3 , 4 The excess oxalic acid was measured with titration using 0.02 M KMnO 4 according to the standard procedure. The ammonia content was removed with the addition of 10% NaOH, and the air/ammonia mixture was sucked out through a sulfuric acid solution using a vacuum (in order to avoid ammonia oxidation by the permanganate, we could not boil off the ammonia by heating).…”

Section: Methodsmentioning

confidence: 99%

Solid-Phase Quasi-Intramolecular Redox Reaction of [Ag(NH₃)₂]MnO₄: An Easy Way to Prepare Pure AgMnO₂

et al. 2021

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Two monoclinic polymorphs of [Ag(NH 3 ) 2 ]MnO 4 containing a unique coordination mode of permanganate ions were prepared, and the high-temperature polymorph was used as a precursor to synthesize pure AgMnO 2 . The hydrogen bonds between the permanganate ions and the hydrogen atoms of ammonia were detected by IR spectroscopy and single-crystal X-ray diffraction. Under thermal decomposition, these hydrogen bonds induced a solid-phase quasi-intramolecular redox reaction between the [Ag(NH 3 ) 2 ] + cation and MnO 4 – anion even before losing the ammonia ligand or permanganate oxygen atom. The polymorphs decomposed into finely dispersed elementary silver, amorphous MnO x compounds, and H 2 O, N 2 and NO gases. Annealing the primary decomposition product at 573 K, the metallic silver reacted with the manganese oxides and resulted in the formation of amorphous silver manganese oxides, which started to crystallize only at 773 K and completely transformed into AgMnO 2 at 873 K.

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An unknown component of a selective and mild oxidant: structure and oxidative ability of a double salt-type complex having κ¹O-coordinated permanganate anions and three- and four-fold coordinated silver cations

Abstract: A compound having redox-active permanganate and complexed silver ions with reducing pyridine ligands is used as a mild organic and as a precursor for nanocatalyst synthesis in a low-temperature solid-phase quasi-intramolecular redox reaction.

Cited by 24 publications

References 50 publications

Thermal analysis of solvatomorphic decakis (dimethylammonium) dihydrogendodecatungstate hydrates

Thermal analysis of solvatomorphic decakis (dimethylammonium) dihydrogendodecatungstate hydrates

Thermal and spectroscopic studies on a double-salt-type pyridine–silver perchlorate complex having κ1-O coordinated perchlorate ions

Solid-Phase Quasi-Intramolecular Redox Reaction of [Ag(NH₃)₂]MnO₄: An Easy Way to Prepare Pure AgMnO₂

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An unknown component of a selective and mild oxidant: structure and oxidative ability of a double salt-type complex having κ1O-coordinated permanganate anions and three- and four-fold coordinated silver cations

Abstract: A compound having redox-active permanganate and complexed silver ions with reducing pyridine ligands is used as a mild organic and as a precursor for nanocatalyst synthesis in a low-temperature solid-phase quasi-intramolecular redox reaction.

Cited by 24 publications

References 50 publications

Thermal analysis of solvatomorphic decakis (dimethylammonium) dihydrogendodecatungstate hydrates

Thermal analysis of solvatomorphic decakis (dimethylammonium) dihydrogendodecatungstate hydrates

Thermal and spectroscopic studies on a double-salt-type pyridine–silver perchlorate complex having κ1-O coordinated perchlorate ions

Solid-Phase Quasi-Intramolecular Redox Reaction of [Ag(NH3)2]MnO4: An Easy Way to Prepare Pure AgMnO2

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An unknown component of a selective and mild oxidant: structure and oxidative ability of a double salt-type complex having κ¹O-coordinated permanganate anions and three- and four-fold coordinated silver cations

Solid-Phase Quasi-Intramolecular Redox Reaction of [Ag(NH₃)₂]MnO₄: An Easy Way to Prepare Pure AgMnO₂