Thermal behavior of platinum fluorides: I. Saturated vapor pressure of platinum tetrafluoride

Никитин, М. И.; Karpukhina, E. N.

doi:10.1134/s0036023607030072

Cited by 7 publications

(5 citation statements)

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“…Such results are in contrast with those obtained to gas phase PtF 6 , which is paramagnetic in the solid state and diamaganetic in the gas phase [1].…”

contrasting

confidence: 54%

“…Such diamagnetic nature for PtF 6 was also predicted based on four component Dirac molecular Hartree-Fock and density functional theory (DFT) and the two component zeroth order regular approach (ZORA) including spin orbit interaction calculations, despite the fact that some criticism was expressed for such conclusion [9][10][11][12][13].…”

mentioning

confidence: 99%

“…As shown to PtF 6 [1], thermochemical data can be of paramount importance to a fully understanding of the properties of such compounds. It was proved that whereas solid state PtF 6 is paramagnetic, gas phase platinum hexafluoride is, indeed, diamagnetic, because a relativistic effect [1].…”

mentioning

confidence: 99%

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Relativistic contribution: an electronic explanation to the thermal disproportionation of PtF5

Farias¹

2017

Preprint

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<div> In the present work, is performed a computational thermochemical study of platinum tetrafluoride (PtF4) and platinum pentafluoride (PtF5). The results are compared to those previously [1] obtained to PtF6 as well as experimental data. Is concluded that in gaseous phase PtF4 and PtF5 retain their structures and number of unpaired electrons exhibited in the solid phase. Furthermore, is proposed that the generally accepted t2g5eg0 configuration to Pt5+ is not correct. Based on the calculated results, an energy diagram is proposed to PtF5, which explain why, upon heating, platinum pentafluoride disproportionates readily [7]: 2PtF5 → PtF4 + PtF6, providing a clear, elegant and straightforward explanation to the thermal instability of PtF5 as consequence of the electronic configuration. </div>

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“…Such results are in contrast with those obtained to gas phase PtF 6 , which is paramagnetic in the solid state and diamaganetic in the gas phase [1].…”

contrasting

confidence: 54%

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confidence: 99%

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Relativistic contribution: an electronic explanation to the thermal disproportionation of PtF5

Farias¹

2017

Preprint

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“…The heat of formation of OsF 6 is not known and that of IrF 6 , estimated in 1929 as −130 kcal/mol from the temperature rise during its preparation, is probably not reliable. The heat of formation of PtF 6 was determined by Knudsen-cell mass spectrometry to be −161.6 ± 6.7 kcal/mol and calculated from calorimetric literature data to be −160.6 ± 1.5 kcal/mol …”

Section: Introductionmentioning

confidence: 99%

“…The heat of formation of PtF 6 was determined by Knudsen-cell mass spectrometry to be -161.6 ( 6.7 kcal/ mol 35 and calculated from calorimetric literature data to be -160.6 ( 1.5 kcal/mol. 36 A number of theoretical studies have predicted the electron affinities (EA) of the metal hexafluorides. Gutsev and Boldyrev 37,38 used the non-relativistic XR method to calculate electron affinities for the MF 6 molecules relative to the experimental value 8 of 3.50 eV for WF 6 .…”

Section: Introductionmentioning

confidence: 99%

Third Row Transition Metal Hexafluorides, Extraordinary Oxidizers, and Lewis Acids: Electron Affinities, Fluoride Affinities, and Heats of Formation of WF₆, ReF₆, OsF₆, IrF₆, PtF₆, and AuF₆

et al. 2010

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High level electronic structure calculations were used to evaluate reliable, self-consistent thermochemical data sets for the third 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 which are a direct measure for the oxidizer strength increase monotonically from WF(6) to AuF(6), with PtF(6) and AuF(6) being extremely powerful oxidizers. The inclusion of spin orbit corrections is necessary to obtain the correct qualitative order for the electron affinities. The calculated electron affinities increase with increasing atomic number, are in good agreement with the available experimental values, and are as follows: WF(6) (3.15 eV), ReF(6) (4.58 eV), OsF(6) (5.92 eV), IrF(6) (5.99 eV), PtF(6) (7.09 eV), and AuF(6) (8.20 eV). A wide range of density functional theory exchange-correlation functionals were also evaluated, and only three gave satisfactory results. The corresponding pentafluorides are extremely strong Lewis acids, with OsF(5), IrF(5), PtF(5), and AuF(5) significantly exceeding the acidity of SbF(5). The optimized geometries of the corresponding MF(7)(-) anions for W through Ir are classical MF(7)(-) anions with M-F bonds; however, for PtF(7)(-) and AuF(7)(-) non-classical anions were found with a very weak external F-F bond between an MF(6)(-) fragment and a fluorine atom. These two anions are text book examples for "superhalogens" and can serve as F atom sources under very mild conditions, explaining the ability of PtF(6) to convert NF(3) to NF(4)(+), ClF(5) to ClF(6)(+), and Xe to XeF(+) and why Bartlett failed to observe XePtF(6) as the reaction product of the PtF(6)/Xe reaction.

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Matrix Isolation Spectroscopic and Relativistic Quantum Chemical Study of Molecular Platinum Fluorides PtF_n (n=1–6) Reveals Magnetic Bistability of PtF₄

Senges

Wodyński

et al. 2021

Chemistry A European J

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Molecular platinum fluorides PtFn, n=1–6, are prepared by two different routes, photo‐initiated fluorine elimination from PtF6 embedded in solid noble‐gas matrices, and the reaction of elemental fluorine with laser‐ablated platinum atoms. IR spectra of the reaction products isolated in rare‐gas matrices under cryogenic conditions provide, for the first time, experimental vibrational frequencies of molecular PtF3, PtF4 and PtF5. Photolysis of PtF6 enabled a highly efficient and almost quantitative formation of molecular PtF4, whereas both PtF5 and PtF3 were formed simultaneously by subsequent UV irradiation of PtF4. The vibrational spectra of these molecular platinum fluorides were assigned with the help of one‐ and two‐component quasirelativistic DFT computation to account for scalar relativistic and spin–orbit coupling effects. Competing Jahn‐Teller and spin–orbit coupling effects result in a magnetic bistability of PtF4, for which a spin‐triplet (3B2g, D2h) coexists with an electronic singlet state (1A1g, D4h) in solid neon matrices.

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Thermal behavior of platinum fluorides: I. Saturated vapor pressure of platinum tetrafluoride

Cited by 7 publications

References 3 publications

Relativistic contribution: an electronic explanation to the thermal disproportionation of PtF5

Relativistic contribution: an electronic explanation to the thermal disproportionation of PtF5

Third Row Transition Metal Hexafluorides, Extraordinary Oxidizers, and Lewis Acids: Electron Affinities, Fluoride Affinities, and Heats of Formation of WF₆, ReF₆, OsF₆, IrF₆, PtF₆, and AuF₆

Matrix Isolation Spectroscopic and Relativistic Quantum Chemical Study of Molecular Platinum Fluorides PtF_n (n=1–6) Reveals Magnetic Bistability of PtF₄

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Thermal behavior of platinum fluorides: I. Saturated vapor pressure of platinum tetrafluoride

Cited by 7 publications

References 3 publications

Relativistic contribution: an electronic explanation to the thermal disproportionation of PtF5

Relativistic contribution: an electronic explanation to the thermal disproportionation of PtF5

Third Row Transition Metal Hexafluorides, Extraordinary Oxidizers, and Lewis Acids: Electron Affinities, Fluoride Affinities, and Heats of Formation of WF6, ReF6, OsF6, IrF6, PtF6, and AuF6

Matrix Isolation Spectroscopic and Relativistic Quantum Chemical Study of Molecular Platinum Fluorides PtFn (n=1–6) Reveals Magnetic Bistability of PtF4

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Third Row Transition Metal Hexafluorides, Extraordinary Oxidizers, and Lewis Acids: Electron Affinities, Fluoride Affinities, and Heats of Formation of WF₆, ReF₆, OsF₆, IrF₆, PtF₆, and AuF₆

Matrix Isolation Spectroscopic and Relativistic Quantum Chemical Study of Molecular Platinum Fluorides PtF_n (n=1–6) Reveals Magnetic Bistability of PtF₄