The electron affinity of platinum hexafluoride

Никитин, М. И.; Sidorov, Lev N.; Korobov, M.V.

doi:10.1016/0020-7381(81)80104-0

Cited by 19 publications

(5 citation statements)

References 7 publications

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“…Our calculated electron affinities lie around 7 eV, which is in excellent agreement with the most recent experimental value by Korobov et al Clearly, earlier values of 8.0 and 9.06 eV can be discarded. , Not surprisingly, the difference between the calculated vertical and adiabatic EAs is even smaller for PtF 6 than for PtF 4 . The optimized structure for octahedral PtF 6 - has a bond length of 1.927 Å.…”

Section: Resultssupporting

confidence: 91%

Structure and Electron Affinity of Platinum Fluorides

Wesendrup

Schwerdtfeger

2001

Inorg. Chem.

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The structure, stability, and electron affinity of the even numbered molecular platinum fluorides PtF(2)(n) (n = 1-4) were studied by scalar relativistic density functional and coupled cluster methods. The di, tetra, and hexafluorides possess triplet ground states, while PtF(8) is a singlet. Formation of the latter from PtF(6) and F(2) is found to be endothermic. Differences between adiabiatic and vertical electron affinities are only significant for PtF(2).

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Section: Resultssupporting

confidence: 91%

Structure and Electron Affinity of Platinum Fluorides

Wesendrup

Schwerdtfeger

2001

Inorg. Chem.

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“…This stability of AuF 6 - is in agreement with the large electron affinity, E (AuF 6 ), calculated by Miyoshi and Sakai of 9.56 eV. The higher nuclear charge of gold must be the most important factor in the greater oxidation resistance of AuF 6 - relative to PtF 6 - the ionization potential of which − (= E (PtF 6 )) is ∼ 8 eV, but the more favorable exchange energy of the dt 2g 6 configuration of Au(V) relative to the dt 2g 5 configuration of Pt(V) must also contribute. The tighter binding of all electrons in AuF 6 - versus PtF 6 - is seen in the smaller effective volume of the former (see Table ).…”

Section: Resultssupporting

confidence: 87%

“…The salts have similar unit cells 6,16,47 and stability with respect to dissociation. In harmony with these similarities the electron affinity of RuF 6 should be close to that of PtF 6 [34][35][36] which is ∼8 eV. It might have been expected, therefore, that the second electron affinity would also have nearly the same value for both ions.…”

Section: Resultsmentioning

confidence: 62%

Room Temperature Syntheses of AuF₆^- and PtF₆^- Salts, Ag⁺AuF₆^-, Ag²⁺PtF₆^2-, and Ag²⁺PdF₆²^-, and an Estimate for E(MF₆^-) [M = Pt, Pd]

et al. 1999

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Solutions of AuF4 - or PtF6 2- salts, prepared from the metals at ∼20 °C, in liquid anhydrous hydrogen fluoride (aHF), made basic with alkali fluorides, are further oxidized by photodissociated F2 (visible or near-UV light) to give AuF6 - or PtF6 - salts, including O2 +AuF6 - (with O2 in the F2). Similar photochemical oxidation of PdF6 2- salts does not occur. This new synthetic approach has provided LiAuF6 and LiPtF6 for the first time, each of which has the LiSbF6 type (R3̄) structure with (hexagonal cell): LiAuF6, a = 4.9953(9) Å, c = 13.704(3) Å, V/Z = 98.71(6) Å3; LiPtF6, a = 5.0236(7) Å, c = 13.623(2) Å, V/Z = 99.25(5) Å3. Interaction of AuF6 - with Ag+ gives Ag+AuF6 - (R3̄, a = 5.283(3) Å, c = 15.053(6) Å, V/Z = 121.3(2) Å3), whereas PtF6 2- or PdF6 2- stabilize Ag2+ as Ag2+Pt(Pd)F6 2- (R3̄; AgPtF6: a = 5.049(8) Å, c = 14.46(2) Å, V/Z = 106.4(5) Å3; and AgPdF6, a = 5.00(4) Å, c = 14.6(2) Å, V/Z = 105(3) Å3). New cubic modifications (probable space group Ia3) have been found for AgMF6 (M, a value, Å): Ru, 9.653(10); Os, 9.7318(9); Ir, 9.704(2). The preference for Ag2+Pt(Pd)F6 2- over Ag+Pt(Pd)F6 - is attributed to a second electron affinity of Pt(Pd)F6, E(Pt(Pd)F6 -)> 60 kcal mol-1.

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“…For example, the equilibrium shown in eq 79 was identified in the vapor PtF4 + PtF<f -PtF4" + PtF6 (79) over a MnF3-MnF2-Pt mixture and was used to determine the electron affinity of PtF6 to be 8.0 ± 0.3 eV-a value which, at the time, was noted as being the highest EA known among all inorganic molecules. 120 ICR techniques are also amenable to the study of fluoride-ionand electron-transfer reactions of transition-metal polyfluorides, albeit only the most volatile ones since the ICR is normally operated at (or near) room temperature. George and Beauchamp investigated the gas-phase ion-molecule reactions of WF6 with a variety of potential fluorideand electron-donor anions.…”

Section: Reactions Of Negative Ions With Neutral Transition-metal Com...mentioning

confidence: 99%