Reactions of complex fluorides of some 3d metals in anhydrous hydrogen fluoride

Court, T. L.; Dove, Michael F. A.

doi:10.1039/c29710000726

Cited by 23 publications

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“…MnF 4 was first described by Hoppe and co-workers. The blue compound is more hygroscopic than MnF 3 . , It can be synthesized by the direct fluorination of Mn above 300 °C, , by a Lewis acid–base reaction of e.g., AsF 5 with [MnF 6 ] 2– anions in anhydrous HF, by thermal decomposition of KrF 2 ·MnF 4 or 2KrF 2 ·MnF 4 , or photochemically from a mixture of MnF 3 and F 2 in anhydrous HF . Two polymorphs of MnF 4 are known.…”

Section: Introductionmentioning

confidence: 99%

Syntheses and Characterization of the Mixed-Valent Manganese(II/III) Fluorides Mn₂F₅ and Mn₃F₈

et al. 2021

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We obtained single crystals of the binary mixed-valent fluorides Mn2F5 and Mn3F8 using a high-pressure/high-temperature approach. Mn2F5 crystallizes isotypic to CaCrF5 in the monoclinic space group C2/c (No. 15), with a = 8.7078(8) Å, b = 6.1473(6) Å, c = 7.7817(7) Å, β = 117.41(1)°, V = 369.80(6) Å3, Z = 4, and mC28 at T = 173 K. Mn3F8 crystallizes in the monoclinic space group P21 (No. 4) with a = 5.5253(2) Å, b = 4.8786(2) Å, c = 9.9124(4) Å, β = 92.608(2)°, V = 266.92(2) Å3, Z = 2, and mP22 at T = 183 K and presents a new structure type. Crystal-chemical reasoning, CHARDI calculations, and quantum-chemical calculations allowed for the assignment of the oxidation states of the Mn atoms. In both bulk compounds, MnF2 was present as an impurity, as evidenced by powder X-ray diffraction and IR and Raman spectroscopy.

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Section: Introductionmentioning

confidence: 99%

Syntheses and Characterization of the Mixed-Valent Manganese(II/III) Fluorides Mn₂F₅ and Mn₃F₈

et al. 2021

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“…For M = Mn, the formation of MnF 4 was reported. [5] In 1980 its enthalpy of formation was investigated. [6] In 1986, one hundred years after the discovery and successful isolation and characterization of elemental fluorine by Henry Moissan, [7] Karl Otto Christe succeeded in the chemical synthesis of elemental fluorine by thermal decomposition of MnF 4 prepared by starting materials that cupied in the VF 3 structure, are grouped together in the shape of a "star" with approximate D 3h symmetry.…”

Section: Introductionmentioning

confidence: 99%

“…In 1962 R. Hoppe, W. Dähne , and W. Klemm synthesized the compound MnF 4 from the reaction of MnF 3 in a flow of F 2 at 300 °C and obtained it as a pale blueish‐grey powder, In 1963 H. Roesky and O. Glemser reported on a new synthesis of MnF 4 in a fluidized bed of Mn metal powder at a temperature of circa 600 °C using F 2 , . In the year 1971 the reaction of M F 6 2– with AsF 5 in anhydrous hydrogen fluoride (aHF) was investigated, and the chemical generation of F 2 and fluorination of Xe for M = Co, Ni, Cu was observed. For M = Mn, the formation of MnF 4 was reported .…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Characterization of Manganese Tetrafluoride β‐MnF₄

Kraus

Ivlev

Bandemehr

et al. 2020

Zeitschrift anorg allge chemie

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The crystal structure of β-MnF 4 has finally been elucidated. It crystallizes in the non-centrosymmetric space group R3c, no. 161, hR360, with the lattice parameters a = 19.390(3), c = 12.940(3) Å, V = 4213.3(14) Å 3 , Z = 72, T = 100 K. It is a 4a ϫ 4a superstructure of the VF 3 (FeF 3) structure type. The Mn atoms are coordinated octahedron-like by F atoms, of which two are bound terminal, while the other act as μ-bridging F atoms to other Mn atoms forming a threedimensional infinite network structure which can be described by the Niggli formula 3 ϱ [MnF 4/2 F 2/1 ]. Voids on the metal sites, which are oc

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“…In complex fluorides, the removal of a fluoride ion from the central atom increases its effective electronegativity. Consequently, the oxidizing power of a compound in a given oxidation state increases in the order anion < neutral molecule < cation, and high oxidation state anions are more stable and can be prepared more easily than the corresponding cations. − …”

Section: Introductionmentioning

confidence: 99%

Novel Synthesis of ClF₆⁺and BrF₆⁺Salts

Schroer

2001

Inorg. Chem.

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For a compound in a given oxidation state, its oxidizing strength increases from its anion to the neutral parent molecule to its cation. Similarly, an anion is more easily oxidized than its neutral parent molecule, which in turn is more easily oxidized than its cation. This concept was systematically exploited in our search for new superoxidizers. Transition metal fluoride anions were prepared in their highest known oxidation states by high temperature/high pressure fluorinations with elemental fluorine and subsequently converted to their more strongly oxidizing cations by a displacement reaction with a strong Lewis acid. The application of this principle resulted in new syntheses for ClF(6)(+)AsF(6)(-) and BrF(6)(+)AsF(6)(-) using the highly reactive and thermally unstable NiF(3)(+) cation that was prepared from the reaction of the NiF(6)(2)(-) anion with AsF(5) in anhydrous HF. Attempts to prepare the known KrF(+) and ClO(2)F(2)(+) cations and the yet unknown XeF(7)(+) cation by the same method were unsuccessful. The results from this and previous studies show that NiF(3)(+) is a stronger oxidative fluorinator than PtF(6), but whether its oxidizing strength exceeds that of KrF(+) remains unclear. Its failure to oxidize Kr to KrF(+) might have been due to unfavorable reaction conditions. Its failure to oxidize ClO(2)F to ClO(2)F(2)(+), in spite of its favorable oxidizer strength, is attributed to the high Lewis basicity of ClO(2)F which results in a rapid displacement reaction of NiF(3)(+) by ClO(2)F, thus generating the weaker oxidizer NiF(4) and the more difficult to oxidize substrate ClO(2)(+). Therefore, the general applicability of this approach appears to be limited to substrates that exhibit a weaker Lewis basicity than the neutral transition metal parent molecule. Compared to KrF(+)- or PtF(6)-based oxidations, the NiF(3)(+) system offers the advantages of commercially available starting materials and higher yields, but product purification can be more difficult and tedious than for KrF(+).

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Reactions of complex fluorides of some 3d metals in anhydrous hydrogen fluoride

Cited by 23 publications

References 0 publications

Syntheses and Characterization of the Mixed-Valent Manganese(II/III) Fluorides Mn₂F₅ and Mn₃F₈

Syntheses and Characterization of the Mixed-Valent Manganese(II/III) Fluorides Mn₂F₅ and Mn₃F₈

Synthesis and Characterization of Manganese Tetrafluoride β‐MnF₄

Novel Synthesis of ClF₆⁺and BrF₆⁺Salts

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Reactions of complex fluorides of some 3d metals in anhydrous hydrogen fluoride

Cited by 23 publications

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Syntheses and Characterization of the Mixed-Valent Manganese(II/III) Fluorides Mn2F5 and Mn3F8

Syntheses and Characterization of the Mixed-Valent Manganese(II/III) Fluorides Mn2F5 and Mn3F8

Synthesis and Characterization of Manganese Tetrafluoride β‐MnF4

Novel Synthesis of ClF6+and BrF6+Salts

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Syntheses and Characterization of the Mixed-Valent Manganese(II/III) Fluorides Mn₂F₅ and Mn₃F₈

Syntheses and Characterization of the Mixed-Valent Manganese(II/III) Fluorides Mn₂F₅ and Mn₃F₈

Synthesis and Characterization of Manganese Tetrafluoride β‐MnF₄

Novel Synthesis of ClF₆⁺and BrF₆⁺Salts