Dynamic disorder in the high-temperature polymorph of bis[diamminesilver(I)] sulfate—reasons and consequences of simultaneous ammonia release from two different polymorphs

Bereczki, Laura; Fogaça, Lara Alexandre; Dürvanger, Zsolt; Harmat, V.; Németh, Gergely; Holló, Berta Barta; Petruševski, Vladimir M.; Bódis, Eszter; Farkas, Attila; Szilágyi, Imre Miklós; Kótai, László

doi:10.1080/00958972.2021.1953489

Cited by 11 publications

(7 citation statements)

References 35 publications

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“…The symmetric deformation mode ν s (N-H) of compound 3-Mn showed two main types of ammonia ligated with different strengths to the central Co III -ion. A relative bond strength parameter (ε) for the ammonia molecules in ammine complexes was defined by Grinberg [27,28]. The parameter (ε) was found to be 0.88 and 0.80 as the two types of coordinated ammonia molecules gave two different δ s (N-H) bands in the IR spectrum of compound 3-Mn.…”

Section: Ligand Vibrationsmentioning

confidence: 99%

“…Thus, the bond strength difference between the two main types of coordinated ammonia molecules in compound 3-Mn is ~10%. This difference may be attributed to the change in the strength of the Co-N bond (apical or equatorial position); however, the electron density change caused by this difference might be attributed to the difference between the hydrogen bond strength of each ammonia molecule, which can play a crucial role in the value of the Grinberg parameter [2,28]. The positions of N-H stretching and deformation N-H modes in the IR spectrum of compound 3-Mn did not give unambiguous information about the presence and strength of hydrogen bonds in the compound 3-Mn.…”

Section: Ligand Vibrationsmentioning

confidence: 99%

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Multi-Centered Solid-Phase Quasi-Intramolecular Redox Reactions of [(Chlorido)Pentaamminecobalt(III)] Permanganate—An Easy Route to Prepare Phase Pure CoMn2O4 Spinel

et al. 2022

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We synthesized and structurally characterized the previously unknown [Co(NH3)5Cl](MnO4)2 complex as the precursor of CoMn2O4. The complex was also deuterated, and its FT-IR, far-IR, low-temperature Raman and UV-VIS spectra were measured as well. The structure of the complex was solved by single-crystal X-ray diffraction and the 3D-hydrogen bonds were evaluated. The N-H…O-Mn hydrogen bonds act as redox centers to initiate a solid-phase quasi-intramolecular redox reaction even at 120 °C involving the Co(III) centers. The product is an amorphous material, which transforms into [Co(NH3)5Cl]Cl2, NH4NO3, and a todorokite-like solid Co-Mn oxide on treatment with water. The insoluble residue may contain {Mn4IIIMnIV2O12}n4n-, {Mn5IIIMnIVO12}n5n- or {MnIII6O12}n6n- frameworks, which can embed 2 × n (CoII and/or CoIII) cations in their tunnels, respectively, and 4 × n ammonia ligands are coordinated to the cobalt cations. The decomposition intermediates decompose on further heating via a series of redox reactions, forming a solid CoIIMIII2O4 spinel with an average size of 16.8 nm, and gaseous N2, N2O and Cl2. The CoMn2O4 prepared in this reaction has photocatalytic activity in Congo red degradation with UV light. Its activity strongly depends on the synthesis conditions, e.g., Congo red was degraded 9 and 13 times faster in the presence of CoMn2O4 prepared at 550 °C (in air) or 420 °C (under N2), respectively.

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Section: Ligand Vibrationsmentioning

confidence: 99%

Section: Ligand Vibrationsmentioning

confidence: 99%

Multi-Centered Solid-Phase Quasi-Intramolecular Redox Reactions of [(Chlorido)Pentaamminecobalt(III)] Permanganate—An Easy Route to Prepare Phase Pure CoMn2O4 Spinel

et al. 2022

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“…The heat-induced quasi-intramolecular redox reactions of [ML n ](XO 4 ) m complexes containing reducing ligands and oxidizing anions (where M = Cu, Zn, Cd, Co; L = NH 3 or pyridine, n = 2–6, and m = 0.5–3, and X = Mn, Cl, S, or Mo) in a solid phase ensure a convenient way to prepare simple or mixed-transition metal oxides with nanometer-sized particles. − These oxides, including nanosized iron oxide composites, − are active catalysts in various industrially important processes as their structures contain defects and their metallic components have variable valence states. − …”

Section: Introductionmentioning

confidence: 99%

Thermally Induced Solid-Phase Quasi-Intramolecular Redox Reactions of [Hexakis(urea-O)iron(III)] Permanganate: An Easy Reaction Route to Prepare Potential (Fe,Mn)O_x Catalysts for CO₂ Hydrogenation

et al. 2022

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Research on new reaction routes and precursors to prepare catalysts for CO 2 hydrogenation has enormous importance. Here, we report on the preparation of the permanganate salt of the urea-coordinated iron(III), [hexakis(urea- O )iron(III)]permanganate ([Fe(urea-O) 6 ](MnO 4 ) 3 ) via an affordable synthesis route and preliminarily demonstrate the catalytic activity of its (Fe,Mn)O x thermal decomposition products in CO 2 hydrogenation. [Fe(urea-O) 6 ](MnO 4 ) 3 contains O-coordinated urea ligands in octahedral propeller-like arrangement around the Fe 3+ cation. There are extended hydrogen bond interactions between the permanganate ions and the hydrogen atoms of the urea ligands. These hydrogen bonds serve as reaction centers and have unique roles in the solid-phase quasi-intramolecular redox reaction of the urea ligand and the permanganate anion below the temperature of ligand loss of the complex cation. The decomposition mechanism of the urea ligand (ammonia elimination with the formation of isocyanuric acid and biuret) has been clarified. In an inert atmosphere, the final thermal decomposition product was manganese-containing wuestite, (Fe,Mn)O, at 800 °C, whereas in ambient air, two types of bixbyite (Fe,Mn) 2 O 3 as well as jacobsite (Fe,Mn) T-4 (Fe,Mn) OC-6 2 O 4 ), with overall Fe to Mn stoichiometry of 1:3, were formed. These final products were obtained regardless of the different atmospheres applied during thermal treatments up to 350 °C. Disordered bixbyite formed first with inhomogeneous Fe and Mn distribution and double-size supercell and then transformed gradually into common bixbyite with regular structure (and with 1:3 Fe to Mn ratio) upon increasing the temperature and heating time. The (Fe,Mn)O x intermediates formed under various conditions showed catalytic effect in the CO 2 hydrogenation reaction with <57.6% CO 2 conversions and <39.3% hydrocarbon yields. As a mild solid-phase oxidant, hexakis(urea- O )iron(III) permanganate, was found to be selective in the transformation of (un)substituted benzylic alcohols into benzaldehydes and benzonitriles.

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“…The classical analytical and basic instrumental measurements were taken using methods and instruments described in detail in our earlier papers [1][2][3][4][5][6][7]. The most essential conditions of the measurement methods are listed below.…”

Section: Methodsmentioning

confidence: 99%

[Hexaamminecobalt(III)] Dichloride Permanganate—Structural Features and Heat-Induced Transformations into (CoII,MnII)(CoIII,MnIII)2O4 Spinels

et al. 2022

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We synthesized and characterized (IR, Raman, UV, SXRD) hexaamminecobalt(III) dichloride permanganate, [Co(NH3)6]Cl2(MnO4) (compound 1) as the precursor of Co–Mn–spinel composites with atomic ratios of Co:Mn = 1:1 and 1:3. The 3D−hydrogen bond network includes N–HO–Mn and N–HCl interactions responsible for solid-phase redox reactions between the permanganate anions and ammonia ligands. The temperature-limited thermal decomposition of compound 1 under the temperature of boiling toluene (110 ∘C) resulted in the formation of (NH4)4Co2Mn6O12. which contains a todorokite-like manganese oxide network (MnII4MnIII2O1210−). The heat treatment products of compounds 1 and [Co(NH3)5Cl](MnO4)2 (2) synthesized previously at 500 ∘C were a cubic and a tetragonal spinel with Co1.5Mn1.5O4 and CoMn2O4 composition, respectively. The heating of the decomposition product of compounds 1 and 2 that formed under refluxing toluene (a mixture with an atomic ratio of Co:Mn = 1:1 and 1:2) and after aqueous leaching ((NH4)4Co2Mn6O12, 1:3 Co:Mn atomic ratio in both cases) at 500 ∘C resulted in tetragonal Co0.75Mn2.25O4 spinels. The Co1.5Mn1.5O4 prepared from compound 1 at 500 ∘C during the solid-phase decomposition catalyzes the degradation of Congo red with UV light. The decomposition rate of the dye was found to be nine times faster than in the presence of the tetragonal CoMn2O4 spinel prepared in the solid-phase decomposition of compound 2. The todorokite-like intermediate prepared from compound 1 under N2 at 115 ∘C resulted in a 54 times faster degradation of Congo red, which is a great deal faster than the same todorokite-like phase that formed from compound 2 under N2.

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Dynamic disorder in the high-temperature polymorph of bis[diamminesilver(I)] sulfate—reasons and consequences of simultaneous ammonia release from two different polymorphs

Cited by 11 publications

References 35 publications

Multi-Centered Solid-Phase Quasi-Intramolecular Redox Reactions of [(Chlorido)Pentaamminecobalt(III)] Permanganate—An Easy Route to Prepare Phase Pure CoMn2O4 Spinel

Multi-Centered Solid-Phase Quasi-Intramolecular Redox Reactions of [(Chlorido)Pentaamminecobalt(III)] Permanganate—An Easy Route to Prepare Phase Pure CoMn2O4 Spinel

Thermally Induced Solid-Phase Quasi-Intramolecular Redox Reactions of [Hexakis(urea-O)iron(III)] Permanganate: An Easy Reaction Route to Prepare Potential (Fe,Mn)O_x Catalysts for CO₂ Hydrogenation

[Hexaamminecobalt(III)] Dichloride Permanganate—Structural Features and Heat-Induced Transformations into (CoII,MnII)(CoIII,MnIII)2O4 Spinels

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Dynamic disorder in the high-temperature polymorph of bis[diamminesilver(I)] sulfate—reasons and consequences of simultaneous ammonia release from two different polymorphs

Cited by 11 publications

References 35 publications

Multi-Centered Solid-Phase Quasi-Intramolecular Redox Reactions of [(Chlorido)Pentaamminecobalt(III)] Permanganate—An Easy Route to Prepare Phase Pure CoMn2O4 Spinel

Multi-Centered Solid-Phase Quasi-Intramolecular Redox Reactions of [(Chlorido)Pentaamminecobalt(III)] Permanganate—An Easy Route to Prepare Phase Pure CoMn2O4 Spinel

Thermally Induced Solid-Phase Quasi-Intramolecular Redox Reactions of [Hexakis(urea-O)iron(III)] Permanganate: An Easy Reaction Route to Prepare Potential (Fe,Mn)Ox Catalysts for CO2 Hydrogenation

[Hexaamminecobalt(III)] Dichloride Permanganate—Structural Features and Heat-Induced Transformations into (CoII,MnII)(CoIII,MnIII)2O4 Spinels

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Thermally Induced Solid-Phase Quasi-Intramolecular Redox Reactions of [Hexakis(urea-O)iron(III)] Permanganate: An Easy Reaction Route to Prepare Potential (Fe,Mn)O_x Catalysts for CO₂ Hydrogenation