Low temperature preparation and uses of potent oxidizers

Bartlett, Neil

doi:10.1016/j.jfluchem.2006.05.021

Cited by 14 publications

(9 citation statements)

References 26 publications

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“…Yields are also still very small. 10 High yields of RuF 6 and RhF 6 have been reported for the fluorination of RuF 5 and RhF 5 with elemental fluorine under static conditions at 230 • C. 11 The least stable RhF 6 has been probably prepared only three or four times since its discovery in 1961.…”

Section: Preparationmentioning

confidence: 99%

The transition metal hexafluorides

Molski

Seppelt

2009

Dalton Trans.

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The nine transition metal hexafluorides present a unique series of closely related compounds. Deviations from octahedral structures are influenced by Jahn-Teller effects and spin orbit coupling. The most pronounced chemical behaviour is the increasing electron affinity in the direction WF(6)--> PtF(6) and MoF(6)--> RuF(6), so that with PtF(6) and RuF(6) values of 7 eV or higher are reached. All hexafluorides can be used as one electron oxidants, starting with mild (WF(6)) up to extreme (PtF(6), RuF(6)) oxidation power.

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Section: Preparationmentioning

confidence: 99%

The transition metal hexafluorides

Molski

Seppelt

2009

Dalton Trans.

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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%

“…Although there is reported evidence for IrO 4 with Ir(VIII) in low-temperature matrices, there was no evidence for Rh(VIII) in analogous experiments . 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. , …”

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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“…Selig and co-workers estimated EA(TcF 6 ) = 6.94 eV based on the correlation of layer spacing and charge transfer with the electron affinities of transition metal hexafluorides intercalated into graphite. Bartlett found that the O 2 RhF 6 salt is less stable toward dissociation to its constituent molecules than O 2 RuF 6 and also has a larger unit cell volume, unlike the lithium salts where the unit cell volume of LiRhF 6 is smaller than that of LiRuF 6 . This led to the conclusion that EA(RuF 6 ) is greater than that of RhF 6 , in contrast to the third row transition metal hexafluorides where the electron affinities increase from WF 6 to AuF 6 …”

Section: Introductionmentioning

confidence: 99%

“… a Final calculated value this work. b Reference . c Reference . d Reference . e Reference . f References and . g Reference . h Reference . i Reference . j Reference . …”

Section: Introductionmentioning

confidence: 99%

Electron Affinities, Fluoride Affinities, and Heats of Formation of the Second Row Transition Metal Hexafluorides: MF₆(M = Mo, Tc, Ru, Rh, Pd, Ag)

et al. 2010

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High-level electronic structure calculations were used to evaluate reliable, self-consistent thermochemical data sets for the second row transition metal hexafluorides. The electron affinities, heats of formation, first (MF(6) --> MF(5) + F) and average M-F bond dissociation energies, and fluoride affinities of MF(6) (MF(6) + F(-) --> MF(7)(-)) and MF(5) (MF(5) + F(-) --> MF(6)(-)) were calculated. The electron affinities are higher than those of the corresponding third row hexafluorides, making them stronger one-electron oxidizers. The calculated electron affinities, in good agreement with the available experimental values, are 4.23 eV for MoF(6), 5.89 eV for TcF(6), 7.01 eV for RuF(6), 6.80 eV for RhF(6), 7.95 eV for PdF(6), and 8.89 eV for AgF(6). The corresponding pentafluorides are also very strong Lewis acids, although their acidities on the pF(-) scale are about one unit lower than those of the third row pentafluorides. The performance of a wide range of DFT exchange-correlation functionals was benchmarked by comparing them to our more accurate CCSD(T) results.

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Low temperature preparation and uses of potent oxidizers

Cited by 14 publications

References 26 publications

The transition metal hexafluorides

The transition metal hexafluorides

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

Electron Affinities, Fluoride Affinities, and Heats of Formation of the Second Row Transition Metal Hexafluorides: MF₆(M = Mo, Tc, Ru, Rh, Pd, Ag)

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Low temperature preparation and uses of potent oxidizers

Cited by 14 publications

References 26 publications

The transition metal hexafluorides

The transition metal hexafluorides

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

Electron Affinities, Fluoride Affinities, and Heats of Formation of the Second Row Transition Metal Hexafluorides: MF6(M = Mo, Tc, Ru, Rh, Pd, Ag)

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

Electron Affinities, Fluoride Affinities, and Heats of Formation of the Second Row Transition Metal Hexafluorides: MF₆(M = Mo, Tc, Ru, Rh, Pd, Ag)