Palladium Chemistry in Molten Alkali Metal Polychalcophosphate Fluxes. Synthesis and Characterization of K4Pd(PS4)2, Cs4Pd(PSe4)2, Cs10Pd(PSe4)4, KPdPS4, K2PdP2S6, and Cs2PdP2Se6

Konstantinos Chondroudis, Mercouri G Kanatzidis, Julien Sayettat, Stéphane Jobic, Raymond Brec

Research output: Contribution to journalArticle

39 Citations (Scopus)

Abstract

The reaction of Pd with a molten mixture of A2Qx/P2Q5/Q (A = K, Q = S, x = 3; A = Cs, Q = Se, x = 1) produced the molecular compounds K4Pd(PS4)2 (I), Cs10Pd(PSe4)2 (II), and Cs10Pd(PSe4)4 (III) and the solid-state KPdPS4 (IV), K2PdP2S6 (V), and Cs2PdP2Se6 (VI). Compounds I-III are air and water sensitive, while IV-VI are air and water stable. All crystals are red or dark red except those of VI, which are black. All of them exhibit a rodlike shape. Compound I crystallizes in the triclinic space group P1̄ (No. 2) with a = 6.380(1) Å, b = 6.897(1) Å, c = 8.999(1) Å, α = 87.777(8)°, β= 81.581(8)°, γ = 84.429(9)°, and Z = 1. Compound II crystallizes in the monoclinic space group P21/c (No. 14) with a = 7.491(2) Å, b = 13.340(2) Å, c = 10.030(3) Å, β= 92.21(2)°, and Z = 2. Compound III crystallizes in the tetragonal space group P42c (No. 112) with a = b = 13.949(2) Å, c = 11.527(2) Å, and Z = 4. Compound IV crystallizes in the tetragonal space group P42/mnm (No. 136) with a = b = 8.5337(2) Å, c = 10.5595(5) Å, and Z = 4. Compound V crystallizes in the orthorombic space group Pnma (No. 62) with a = 15.612(2) Å, b = 7.0724(7) Å, c = 10.080(1) Å, and Z = 4. Compound VI crystallizes in the monoclinic space group C2/c (No. 15) with a = 12.9750(4) Å, b = 8.3282(2) Å, c = 13.0568(1) Å, β = 102.940(2)°, and Z = 4. Compounds I-III contain the discrete complexes [Pd(PQ4)2]4- (Q = S, Se). The mixed salt III contains additional noncoordinating [PSe4]3- units. The structure of IV consists of Pd(II) in square planar sulfur coordination linked by edge-sharing [PS4]3- tetrahedral groups to produce one-dimensional chains. The structures of V and VI feature the [P2Q6]4- (Q = S, Se) group coordinated to the square planar Pd2+ atoms, yielding [PdP2Q6]n2n- chains. Physical characterization was performed with DTA, far-IR spectroscopy, solid-state UV/vis diffuse reflectance spectroscopy, and single-crystal optical transmission.

Original languageEnglish
Pages (from-to)5859-5868
Number of pages10
JournalInorganic Chemistry
Volume36
Issue number25
Publication statusPublished - 1997

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Alkali Metals
Palladium
alkali metals
Molten materials
palladium
chemistry
Fluxes
Water
synthesis
Light transmission
Air
Sulfur
Differential thermal analysis
Infrared spectroscopy
Salts
Single crystals
Spectroscopy
Atoms
Crystals
solid state

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Palladium Chemistry in Molten Alkali Metal Polychalcophosphate Fluxes. Synthesis and Characterization of K4Pd(PS4)2, Cs4Pd(PSe4)2, Cs10Pd(PSe4)4, KPdPS4, K2PdP2S6, and Cs2PdP2Se6. / Chondroudis, Konstantinos; Kanatzidis, Mercouri G; Sayettat, Julien; Jobic, Stéphane; Brec, Raymond.

In: Inorganic Chemistry, Vol. 36, No. 25, 1997, p. 5859-5868.

Research output: Contribution to journalArticle

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title = "Palladium Chemistry in Molten Alkali Metal Polychalcophosphate Fluxes. Synthesis and Characterization of K4Pd(PS4)2, Cs4Pd(PSe4)2, Cs10Pd(PSe4)4, KPdPS4, K2PdP2S6, and Cs2PdP2Se6",
abstract = "The reaction of Pd with a molten mixture of A2Qx/P2Q5/Q (A = K, Q = S, x = 3; A = Cs, Q = Se, x = 1) produced the molecular compounds K4Pd(PS4)2 (I), Cs10Pd(PSe4)2 (II), and Cs10Pd(PSe4)4 (III) and the solid-state KPdPS4 (IV), K2PdP2S6 (V), and Cs2PdP2Se6 (VI). Compounds I-III are air and water sensitive, while IV-VI are air and water stable. All crystals are red or dark red except those of VI, which are black. All of them exhibit a rodlike shape. Compound I crystallizes in the triclinic space group P1̄ (No. 2) with a = 6.380(1) {\AA}, b = 6.897(1) {\AA}, c = 8.999(1) {\AA}, α = 87.777(8)°, β= 81.581(8)°, γ = 84.429(9)°, and Z = 1. Compound II crystallizes in the monoclinic space group P21/c (No. 14) with a = 7.491(2) {\AA}, b = 13.340(2) {\AA}, c = 10.030(3) {\AA}, β= 92.21(2)°, and Z = 2. Compound III crystallizes in the tetragonal space group P42c (No. 112) with a = b = 13.949(2) {\AA}, c = 11.527(2) {\AA}, and Z = 4. Compound IV crystallizes in the tetragonal space group P42/mnm (No. 136) with a = b = 8.5337(2) {\AA}, c = 10.5595(5) {\AA}, and Z = 4. Compound V crystallizes in the orthorombic space group Pnma (No. 62) with a = 15.612(2) {\AA}, b = 7.0724(7) {\AA}, c = 10.080(1) {\AA}, and Z = 4. Compound VI crystallizes in the monoclinic space group C2/c (No. 15) with a = 12.9750(4) {\AA}, b = 8.3282(2) {\AA}, c = 13.0568(1) {\AA}, β = 102.940(2)°, and Z = 4. Compounds I-III contain the discrete complexes [Pd(PQ4)2]4- (Q = S, Se). The mixed salt III contains additional noncoordinating [PSe4]3- units. The structure of IV consists of Pd(II) in square planar sulfur coordination linked by edge-sharing [PS4]3- tetrahedral groups to produce one-dimensional chains. The structures of V and VI feature the [P2Q6]4- (Q = S, Se) group coordinated to the square planar Pd2+ atoms, yielding [PdP2Q6]n2n- chains. Physical characterization was performed with DTA, far-IR spectroscopy, solid-state UV/vis diffuse reflectance spectroscopy, and single-crystal optical transmission.",
author = "Konstantinos Chondroudis and Kanatzidis, {Mercouri G} and Julien Sayettat and St{\'e}phane Jobic and Raymond Brec",
year = "1997",
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TY - JOUR

T1 - Palladium Chemistry in Molten Alkali Metal Polychalcophosphate Fluxes. Synthesis and Characterization of K4Pd(PS4)2, Cs4Pd(PSe4)2, Cs10Pd(PSe4)4, KPdPS4, K2PdP2S6, and Cs2PdP2Se6

AU - Chondroudis, Konstantinos

AU - Kanatzidis, Mercouri G

AU - Sayettat, Julien

AU - Jobic, Stéphane

AU - Brec, Raymond

PY - 1997

Y1 - 1997

N2 - The reaction of Pd with a molten mixture of A2Qx/P2Q5/Q (A = K, Q = S, x = 3; A = Cs, Q = Se, x = 1) produced the molecular compounds K4Pd(PS4)2 (I), Cs10Pd(PSe4)2 (II), and Cs10Pd(PSe4)4 (III) and the solid-state KPdPS4 (IV), K2PdP2S6 (V), and Cs2PdP2Se6 (VI). Compounds I-III are air and water sensitive, while IV-VI are air and water stable. All crystals are red or dark red except those of VI, which are black. All of them exhibit a rodlike shape. Compound I crystallizes in the triclinic space group P1̄ (No. 2) with a = 6.380(1) Å, b = 6.897(1) Å, c = 8.999(1) Å, α = 87.777(8)°, β= 81.581(8)°, γ = 84.429(9)°, and Z = 1. Compound II crystallizes in the monoclinic space group P21/c (No. 14) with a = 7.491(2) Å, b = 13.340(2) Å, c = 10.030(3) Å, β= 92.21(2)°, and Z = 2. Compound III crystallizes in the tetragonal space group P42c (No. 112) with a = b = 13.949(2) Å, c = 11.527(2) Å, and Z = 4. Compound IV crystallizes in the tetragonal space group P42/mnm (No. 136) with a = b = 8.5337(2) Å, c = 10.5595(5) Å, and Z = 4. Compound V crystallizes in the orthorombic space group Pnma (No. 62) with a = 15.612(2) Å, b = 7.0724(7) Å, c = 10.080(1) Å, and Z = 4. Compound VI crystallizes in the monoclinic space group C2/c (No. 15) with a = 12.9750(4) Å, b = 8.3282(2) Å, c = 13.0568(1) Å, β = 102.940(2)°, and Z = 4. Compounds I-III contain the discrete complexes [Pd(PQ4)2]4- (Q = S, Se). The mixed salt III contains additional noncoordinating [PSe4]3- units. The structure of IV consists of Pd(II) in square planar sulfur coordination linked by edge-sharing [PS4]3- tetrahedral groups to produce one-dimensional chains. The structures of V and VI feature the [P2Q6]4- (Q = S, Se) group coordinated to the square planar Pd2+ atoms, yielding [PdP2Q6]n2n- chains. Physical characterization was performed with DTA, far-IR spectroscopy, solid-state UV/vis diffuse reflectance spectroscopy, and single-crystal optical transmission.

AB - The reaction of Pd with a molten mixture of A2Qx/P2Q5/Q (A = K, Q = S, x = 3; A = Cs, Q = Se, x = 1) produced the molecular compounds K4Pd(PS4)2 (I), Cs10Pd(PSe4)2 (II), and Cs10Pd(PSe4)4 (III) and the solid-state KPdPS4 (IV), K2PdP2S6 (V), and Cs2PdP2Se6 (VI). Compounds I-III are air and water sensitive, while IV-VI are air and water stable. All crystals are red or dark red except those of VI, which are black. All of them exhibit a rodlike shape. Compound I crystallizes in the triclinic space group P1̄ (No. 2) with a = 6.380(1) Å, b = 6.897(1) Å, c = 8.999(1) Å, α = 87.777(8)°, β= 81.581(8)°, γ = 84.429(9)°, and Z = 1. Compound II crystallizes in the monoclinic space group P21/c (No. 14) with a = 7.491(2) Å, b = 13.340(2) Å, c = 10.030(3) Å, β= 92.21(2)°, and Z = 2. Compound III crystallizes in the tetragonal space group P42c (No. 112) with a = b = 13.949(2) Å, c = 11.527(2) Å, and Z = 4. Compound IV crystallizes in the tetragonal space group P42/mnm (No. 136) with a = b = 8.5337(2) Å, c = 10.5595(5) Å, and Z = 4. Compound V crystallizes in the orthorombic space group Pnma (No. 62) with a = 15.612(2) Å, b = 7.0724(7) Å, c = 10.080(1) Å, and Z = 4. Compound VI crystallizes in the monoclinic space group C2/c (No. 15) with a = 12.9750(4) Å, b = 8.3282(2) Å, c = 13.0568(1) Å, β = 102.940(2)°, and Z = 4. Compounds I-III contain the discrete complexes [Pd(PQ4)2]4- (Q = S, Se). The mixed salt III contains additional noncoordinating [PSe4]3- units. The structure of IV consists of Pd(II) in square planar sulfur coordination linked by edge-sharing [PS4]3- tetrahedral groups to produce one-dimensional chains. The structures of V and VI feature the [P2Q6]4- (Q = S, Se) group coordinated to the square planar Pd2+ atoms, yielding [PdP2Q6]n2n- chains. Physical characterization was performed with DTA, far-IR spectroscopy, solid-state UV/vis diffuse reflectance spectroscopy, and single-crystal optical transmission.

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