The room temperature preparation of metastable fluorides and potent oxidizers

Žemva, Boris; Bartlett, Neil

doi:10.1016/j.jfluchem.2006.09.017

Cited by 10 publications

(11 citation statements)

References 25 publications

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“…When Ag(II) cations are found in superacidic environments, and in the presence of weakly coordinating anions, they exhibit superb oxidizing properties. This is exemplified by AgF + cations solvated by anhydrous HF acidified with Lewis acids; these species are capable of oxidizing, inter alia, xenon and O 2 while yielding Xe(II) and O + 2 cations, respectively [13]. Since both the first ionization potential of an O 2 molecule and that of a Xe atom exceed 12 eV, Ag(II) cations retain in this electron-deficient environment substantial share (approx.…”

Section: Redox-reduxmentioning

confidence: 99%

Chemistry of silver(II): a cornucopia of peculiarities

Grochala

Mazej

2015

Phil. Trans. R. Soc. A.

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Silver is the heavier congener of copper in the Periodic Table, but the chemistry of these two elements is very different. While Cu(II) is the most common cationic form of copper, Ag(II) is rare and its compounds exhibit a broad range of peculiar physico-chemical properties. These include, but are not limited to: (i) uncommon oxidizing properties, (ii) unprecedented large mixing of metal and ligand valence orbitals, (iii) strong spin-polarization of neighbouring ligands, (iv) record large magnetic superexchange constants, (v) ease of thermal decomposition of its salts with O-, N- or C-ligands, as well as (vi) robust Jahn–Teller effect which is preserved even at high pressure. These intriguing features of the compounds of Ag(II) will be discussed here together with (vii) a possibility of electromerism (electronic tautomerism) for a certain class of Ag(II) salts.

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Section: Redox-reduxmentioning

confidence: 99%

Chemistry of silver(II): a cornucopia of peculiarities

Grochala

Mazej

2015

Phil. Trans. R. Soc. A.

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“…22 In addition to being vital to understanding the limits of chemical stability, the more stable, high oxidation state fluorides can be used as potent oxidizers. 30,31 Of the "missing" hexafluorides, 2 PdF 6 is probably the most surprising, given that all the other 4d and 5d hexafluorides of Groups 6-8 are known, 7,8 including PtF 6 , 32,33 which was instrumental in the development of xenon chemistry as long ago as 1962. 34,35 There appear to be no experimental reports on PdF.…”

Section: Introductionmentioning

confidence: 99%

A Matrix Isolation and Computational Study of Molecular Palladium Fluorides: Does PdF₆ Exist?

et al. 2016

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Palladium atoms generated by thermal evaporation and laser ablation were reacted with and trapped in F2/Ar, F2/Ne, and neat F2 matrices. The products were characterized by electronic absorption and infrared spectroscopy, together with relativistic density functional theory calculations as well as coupled cluster calculations. Vibrational modes at 540 and 617 cm(-1) in argon matrices were assigned to molecular PdF and PdF2, and a band at 692 cm(-1) was assigned to molecular PdF4. A band at 624 cm(-1) can be assigned to either PdF3 or PdF6, with the former preferred from experimental considerations. Although calculations might support the latter assignment, our conclusion is that in these detailed experiments there is no convincing evidence for PdF6.

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“…Their solution chemistry is quite well known in aqueous solutions, hydrofluoric acid, or anhydrous HF. [1][2][3][4][5] We set out to explore the reactions of fluorides with liquid ammonia, which could yield substances like fluoride ammoniates, amine fluorides and amide-or imide fluorides, [6][7][8][9] or even nitride fluorides and nitrides as the final products of these reactions. [10] With the exception of the nitrides, all these classes of compounds are only scarcely known and could feature interesting properties depending on the metal ion.…”

Section: Introductionmentioning

confidence: 99%

The Reactions of Silver, Zirconium, and Hafnium Fluorides with Liquid Ammonia: Syntheses and Crystal Structures of Ag(NH₃)₂F·2NH₃, [M(NH₃)₄F₄]·NH₃ (M = Zr, Hf), and (N₂H₇)F

2009

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By reaction of the tetrafluorides MF4 or the ternary silver fluorides Ag3M2F14 (M = Zr, Hf) with dry liquid ammonia at –40 °C, the pentaammoniates [M(NH3)4F4]·NH3 (1, M = Zr; 2, M = Hf) were obtained, and these compounds represent hitherto unknown molecular inorganic Zr and Hf compounds that simultaneously bear nitrogen and fluorine ligands. The compounds crystallize isotypically in the shape of colorless needles in the tetragonal space group P4/ncc. As a further product [NH4(NH3)]F (3) was isolated in the form of colorless cubes in the orthorhombic space group Pca21. It is the first ammoniate of ammonium fluoride. Ag(NH3)2F·2NH3 (4) can be synthesized either from AgF or AgF2 in liquid ammonia. The compound crystallizes merohedrally twinned in the orthorhombic space group Pnna and represents the first crystallographically characterized diamine silver(I) halide complex. In the latter two structures, free fluoride anions are encountered. The ammoniates are highly temperature‐sensitive and decompose at temperatures above –30 °C due to their ammonia pressure.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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The room temperature preparation of metastable fluorides and potent oxidizers

Cited by 10 publications

References 25 publications

Chemistry of silver(II): a cornucopia of peculiarities

Chemistry of silver(II): a cornucopia of peculiarities

A Matrix Isolation and Computational Study of Molecular Palladium Fluorides: Does PdF₆ Exist?

The Reactions of Silver, Zirconium, and Hafnium Fluorides with Liquid Ammonia: Syntheses and Crystal Structures of Ag(NH₃)₂F·2NH₃, [M(NH₃)₄F₄]·NH₃ (M = Zr, Hf), and (N₂H₇)F

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The room temperature preparation of metastable fluorides and potent oxidizers

Cited by 10 publications

References 25 publications

Chemistry of silver(II): a cornucopia of peculiarities

Chemistry of silver(II): a cornucopia of peculiarities

A Matrix Isolation and Computational Study of Molecular Palladium Fluorides: Does PdF6 Exist?

The Reactions of Silver, Zirconium, and Hafnium Fluorides with Liquid Ammonia: Syntheses and Crystal Structures of Ag(NH3)2F·2NH3, [M(NH3)4F4]·NH3 (M = Zr, Hf), and (N2H7)F

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A Matrix Isolation and Computational Study of Molecular Palladium Fluorides: Does PdF₆ Exist?

The Reactions of Silver, Zirconium, and Hafnium Fluorides with Liquid Ammonia: Syntheses and Crystal Structures of Ag(NH₃)₂F·2NH₃, [M(NH₃)₄F₄]·NH₃ (M = Zr, Hf), and (N₂H₇)F