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

Bereczki, Laura; Petruševski, Vladimir M.; Franguelli, Fernanda Paiva; Béres, Kende Attila; Farkas, Attila; Holló, Berta Barta; Czégény, Zsuzsanna; Szilágyi, Imre Miklós; Kótai, László

doi:10.3390/inorganics10120252

Cited by 7 publications

(23 citation statements)

References 64 publications

(134 reference statements)

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“…It shows that the interactions between the cation A and the permanganate ions are slightly loose, whereas for the cation B, the N-H•••O spike is pronounced. The number of the N-H•••Cl interactions of cation A is higher than that for cation B (indicated by red) [61].…”

Section: Hexammine Complexesmentioning

confidence: 89%

“…Both complexes are slightly soluble in water (0.91 g/100 mL H 2 O at 19 • C for the Zn compound [37]), but their aqueous solutions lose their beautiful purple color, and manganese oxide is quickly deposited [60,61]. Their hydrolysis reaction proceeds in aq.…”

Section: Tetraamminezinc(ii) and [Tetraamminecadmium(ii)] Permanganatesmentioning

confidence: 99%

“…On cooling, small strips of black crystals are deposited, which are washed with a sufficient quantity of water and dried at 50 • C [121]. The chloride compound was prepared at room temperature, which resulted in the same product in 16.4% yield due to the solubility of [hexaammincobalt(III)] dichloride permanganate in water at room temperature (7.89 g/100 mL) [61]. These were also prepared directly from [hexaamminecobalt(III)] salts with 1.5 equivalent of potassium permanganate solutions keeping the solution for 6 h [121].…”

Section: Hexammine Complexesmentioning

confidence: 99%

“…The chloride salt forms red platelets, monoclinic, space group P2 1 /c, a = 13.6133 Å, b = 7.3658 Å, c = 12.3682 Å; β = 108.547 • , Z = 4, D calcd . = 1.983 g/mL, T = 163 K, V = 1175.78 Å 3 [61]. The elementary cell contains four formula units, whereas the asymmetric unit contains two halves of the complex cation, two chloride ions, and one permanganate ion.…”

Section: Hexammine Complexesmentioning

confidence: 99%

“…One of the most promising groups of the above-mentioned complexes is the ammonia complex group [34,[55][56][57][58], especially the complexes with tetraoxometallate anions of the VIIB group (Mn, Tc, Re). These complexes show wide variation in coordination number and geometry, which has an influence on the temperature-initiated redox reactions in these complexes, found not only between the anion and ligand [28,29,37,54,59,60] but in some cases between the oxidizing central ion (e.g., cobalt(III)) and the ammonia as well [61,62]. This in situ ammonia formation, e.g., from urea complexes [11], shows reactions similar to the decomposition of ammonia, with ammonia being released together with the oxidation reaction.…”

Section: Introductionmentioning

confidence: 99%

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Review on the Chemistry of [M(NH3)n](XO4)m (M = Transition Metal, X = Mn, Tc or Re, n = 1–6, m = 1–3) Ammine Complexes

Mehrotra

2023

Inorganics

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The preparation of ammine complexes of transition metals having oxidizing anions such as permanganate and perrhenate ions is a great challenge due to possible reactions between ammonia and oxidizing anions during the synthesis of these materials. However, it has an important role in both the development of new oxidants in organic chemistry and especially in the preparation of mixed-metal oxide catalyst precursors and metal alloys for their controlled temperature decomposition reactions. Therefore, in this paper, synthetic procedures to prepare ammonia complexes of transition metal permanganate, pertechnetate, and perrhenate (the VIIB group tetraoxometallates) salts have been comprehensively reviewed. The available data about these compounds’ structures and spectroscopic properties, including the presence of hydrogen bonds that act as redox reaction centers during thermal decomposition, are given and evaluated in detail. The nature of the thermal decomposition products has also been summarized. The available information about the role of the ammine complexes of transition metal permanganate salts in organic oxidation reactions, such as the oxidation of benzyl alcohols and regeneration of oxo-compounds from oximes and phenylhydrazones, including the kinetics of these processes, has also been collected. Their physical and chemical properties, including the thermal decomposition characteristics of known diammine (Ag(I), Cd, Zn, Cu(II), Ni(II)), triammine (Ag(I)), and simple or mixed ligand tetraammine (Cu(II), Zn, Cd, Ni(II), Co(II), Pt(II), Pd(II), Co(III)), Ru(III), pentaammine (Co(III), Cr(III), Rh(III) and Ir(III)), and hexaammine (Ni(II), Co(III), Cr(III)) complexes of transition metals with tetraoxometallate(VII) anions (M = Mn, Tc and Re), have been summarized. The preparation and properties of some special mixed ligand/anion/cation-containing complexes, such as [Ru(NH3)4(NO)(H2O)](ReO4)2, [Co(NH3)5(H2O)](ReO4)2, [Co(NH3)5X](MnO4)2 (X = Cl, Br), [Co(NH3)6]Cl2(MnO4), [Co(NH3)5ReO4]X2 (X = Cl, NO3, ClO4, ReO4), and K[Co(NH3)6]Cl2(MnO4)2, are also included.

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Section: Hexammine Complexesmentioning

confidence: 89%

Section: Tetraamminezinc(ii) and [Tetraamminecadmium(ii)] Permanganatesmentioning

confidence: 99%

Section: Hexammine Complexesmentioning

confidence: 99%

Section: Hexammine Complexesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Review on the Chemistry of [M(NH3)n](XO4)m (M = Transition Metal, X = Mn, Tc or Re, n = 1–6, m = 1–3) Ammine Complexes

Mehrotra

2023

Inorganics

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Review on the Chemistry of [M(NH3)n](XO4)m (M=Transition Metal, X=Mn, Tc or Re, n=1-6, m=1-3) Ammine Complexes

Mehrotra¹

2023

Preprint

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The preparation of transition metal salt ammine complexes having oxidizing anions is a great challenge due to the reaction between the ammonia and oxidizing anions during the synthesis of these materials. However, they have an important role in the development of new oxidants in organic chemistry and especially as precursors in the preparation of mixed metal oxides and alloys in controlled temperature thermal decomposition reactions. Therefore, the synthetic procedures to prepare the complexes of transition metal permanganate, pertechnetate, and perrhenate (VIIB group tetraoxometallates) salts with ammonia as ligand or co-ligand have been comprehensively reviewed. The available data about the structure and spectroscopic properties of these compounds, including the hydrogen bonds that act as redox reaction centers under their thermal decomposition are given and evaluated. Their thermal decomposition processes and products have been summarized. The available pieces of information about their role in organic oxidation reactions like the oxidation of benzyl alcohols, and regeneration of oxo-compounds from oximes and phenylhydrazones including the kinetics of these processes have also been collected.

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Crystal Structure of the Octahedral iron(III)-Nitrate Complexes with Isomer Dimethylurea Ligands

Béres¹,

Homonnay²,

Bereczki³

et al. 2023

Preprint

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Three octahedral iron(III) nitrate complexes with dimethylated urea ligand isomers, [hexakis(N,N’-dimethylurea-O)iron(III)] nitrate (compound 1), trans-[diaquatetrakis(N,N-dimethylurea-O)iron(III)] nitrate (compound 2) and [hexakis(N,N-dimethylurea-O)iron(III)] nitrate trihydrate (compound 3) were prepared and characterized with single crystal X-ray diffraction, IR, Raman and UV-VIS methods. In compounds 1 and 3, six dimethylurea ligands coordinate to the central FeIII ion via the oxygen in octahedral geometry and the ligands are arranged in a propeller-like manner, dividing the complex cations into two sides. In compound 1, the dimethylurea propellers screw in the opposite direction on the two sides of the complex and in compound 3, they are arranged with the same handedness on the two sides. The complexes have helical chirality. The two sides of the complex cations differ not only in the rotation direction of the ligands but also in the hydrogen bond formation. On one side of the complex cation, the ligands form intermolecular hydrogen bonds only with the crystal waters, meanwhile on the other side of the complex, the ligands form hydrogen bonds only with the nitrate ions. In compound 2, [Fe(N,N-dimethylurea)4(H2O)2]3+ cations form layers that are separated by interconnected NO3- ions forming a hydrogen bonding system and connecting the complex cations A-s and B-s. The three crystallographically different nitrate ions each form four hydrogen bonds in a way that they have one bidentate O atom and two monodentate O atoms, however, the anions differ in their hydrogen bonding. The spectroscopic characteristics of compound 2 were determined by IR measurements on the deuterated compound 2 as well.

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

Cited by 7 publications

References 64 publications

Review on the Chemistry of [M(NH3)n](XO4)m (M = Transition Metal, X = Mn, Tc or Re, n = 1–6, m = 1–3) Ammine Complexes

Review on the Chemistry of [M(NH3)n](XO4)m (M = Transition Metal, X = Mn, Tc or Re, n = 1–6, m = 1–3) Ammine Complexes

Review on the Chemistry of [M(NH<sub>3</sub>)<sub>n</sub>](XO<sub>4</sub>)<sub>m</sub> (M=Transition Metal, X=Mn, Tc or Re, n=1-6, m=1-3) Ammine Complexes

Crystal Structure of the Octahedral iron(III)-Nitrate Complexes with Isomer Dimethylurea Ligands

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