Room temperature syntheses of AuF6 - and PtF6 - salts, Ag+AuF6 -, Ag2+PtF6 2-, and Ag2+pdF6 2-, and an estimate for E(MF6 -) [M = Pt, Pd]

Oliver Graudejus, S. H. Elder, G. M. Lucier, C. Shen, N. Bartlett

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Abstract

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.

Original languageEnglish (US)
Pages (from-to)2503-2509
Number of pages7
JournalInorganic Chemistry
Volume38
Issue number10
StatePublished - Dec 1 1999
Externally publishedYes

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Salts
salts
room temperature
synthesis
estimates
hexagonal cells
Hydrofluoric Acid
Electron affinity
liquid hydrogen
hydrofluoric acid
Alkalies
electron affinity
Fluorides
Ultraviolet radiation
Temperature
fluorides
alkalies
Metals
Oxidation
oxidation

ASJC Scopus subject areas

  • Inorganic Chemistry

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Room temperature syntheses of AuF6 - and PtF6 - salts, Ag+AuF6 -, Ag2+PtF6 2-, and Ag2+pdF6 2-, and an estimate for E(MF6 -) [M = Pt, Pd]. / Graudejus, Oliver; Elder, S. H.; Lucier, G. M.; Shen, C.; Bartlett, N.

In: Inorganic Chemistry, Vol. 38, No. 10, 01.12.1999, p. 2503-2509.

Research output: Contribution to journalArticle

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title = "Room temperature syntheses of AuF6 - and PtF6 - salts, Ag+AuF6 -, Ag2+PtF6 2-, and Ag2+pdF6 2-, and an estimate for E(MF6 -) [M = Pt, Pd]",
abstract = "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) {\AA}, c = 13.704(3) {\AA}, V/Z = 98.71(6) {\AA}3; LiPtF6, a = 5.0236(7) {\AA}, c = 13.623(2) {\AA}, V/Z = 99.25(5) {\AA}3. Interaction of AuF6 - with Ag+ gives Ag+AuF6 - (R3̄, a = 5.283(3) {\AA}, c = 15.053(6) {\AA}, V/Z = 121.3(2) {\AA}3), whereas PtF6 2- or PdF6 2- stabilize Ag2+ as Ag2+Pt(Pd)F6 2- (R3̄; AgPtF6: a = 5.049(8) {\AA}, c = 14.46(2) {\AA}, V/Z = 106.4(5) {\AA}3; and AgPdF6, a = 5.00(4) {\AA}, c = 14.6(2) {\AA}, V/Z -105(3) {\AA}3). New cubic modifications (probable space group Ia3) have been found for AgMF6 (M, a value, {\AA}): 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.",
author = "Oliver Graudejus and Elder, {S. H.} and Lucier, {G. M.} and C. Shen and N. Bartlett",
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T1 - Room temperature syntheses of AuF6 - and PtF6 - salts, Ag+AuF6 -, Ag2+PtF6 2-, and Ag2+pdF6 2-, and an estimate for E(MF6 -) [M = Pt, Pd]

AU - Graudejus, Oliver

AU - Elder, S. H.

AU - Lucier, G. M.

AU - Shen, C.

AU - Bartlett, N.

PY - 1999/12/1

Y1 - 1999/12/1

N2 - 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.

AB - 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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