10.1021/ic970593n.s001
Konstantinos Chondroudis
Konstantinos
Chondroudis
Mercouri G. Kanatzidis
Mercouri G.
Kanatzidis
Julien Sayettat
Julien
Sayettat
Stéphane Jobic
Stéphane
Jobic
Raymond Brec
Raymond
Brec
Palladium Chemistry in Molten Alkali Metal Polychalcophosphate Fluxes. Synthesis and
Characterization of K<sub>4</sub>Pd(PS<sub>4</sub>)<sub>2</sub>, Cs<sub>4</sub>Pd(PSe<sub>4</sub>)<sub>2</sub>, Cs<sub>10</sub>Pd(PSe<sub>4</sub>)<sub>4</sub>, KPdPS<sub>4</sub>, K<sub>2</sub>PdP<sub>2</sub>S<sub>6</sub>, and
Cs<sub>2</sub>PdP<sub>2</sub>Se<sub>6</sub>
American Chemical Society
1997
Cs 2 PdP 2 Se 6
n 2 n
orthorombic space group Pnma
K 2 PdP 2 S 6
PdP 2 Q 6
P 2 Q 6
crystallize
KPdPS 4
DTA
Molten Alkali Metal Polychalcophosphate Fluxes
UV
4.
III
VI
IV
II
1997-12-03 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Palladium_Chemistry_in_Molten_Alkali_Metal_Polychalcophosphate_Fluxes_Synthesis_and_Characterization_of_K_sub_4_sub_Pd_PS_sub_4_sub_sub_2_sub_Cs_sub_4_sub_Pd_PSe_sub_4_sub_sub_2_sub_Cs_sub_10_sub_Pd_PSe_sub_4_sub_sub_4_sub_KPdPS_sub_4_sub_K_sub_2_sub_PdP_/3619305
The reaction of Pd with a molten mixture of
A<sub>2</sub>Q<i><sub>x</sub></i>/P<sub>2</sub>Q<sub>5</sub>/Q
(A = K, Q = S, <i>x</i> = 3; A = Cs, Q = Se, <i>x</i>
= 1)
produced the molecular compounds
K<sub>4</sub>Pd(PS<sub>4</sub>)<sub>2</sub>
(<b>I</b>),
Cs<sub>4</sub>Pd(PSe<sub>4</sub>)<sub>2</sub>
<b>(II)</b>, and
Cs<sub>10</sub>Pd(PSe<sub>4</sub>)<sub>4</sub>
<b>(III)</b> and the solid-state KPdPS<sub>4</sub> (<b>IV</b>),
K<sub>2</sub>PdP<sub>2</sub>S<sub>6</sub> <b>(V)</b>, and
Cs<sub>2</sub>PdP<sub>2</sub>Se<sub>6</sub>
<b>(VI)</b>. Compounds <b>I</b>−<b>III</b> are
air and water sensitive, while
<b>IV</b>−<b>VI</b> are air and water stable. All
crystals are red or dark red except those of <b>VI</b>, which are
black. All of
them exhibit a rodlike shape. Compound <b>I</b> crystallizes
in the triclinic space group <i>P</i>1̄ (No. 2) with
<i>a</i> = 6.380(1)
Å, <i>b</i> = 6.897(1) Å, <i>c</i> = 8.999(1)
Å, α = 87.777(8)°, β = 81.581(8)°, γ =
84.429(9)°, and <i>Z</i> = 1. Compound
<b>II</b> crystallizes in the monoclinic space group
<i>P</i>2<sub>1</sub>/<i>c</i> (No. 14) with <i>a</i> =
7.491(2) Å, <i>b</i> = 13.340(2) Å, <i>c</i>
=
10.030(3) Å, β = 92.21(2)°, and <i>Z</i> = 2.
Compound <b>III</b> crystallizes in the tetragonal space group
<i>P</i>4̄2<i>c</i> (No. 112)
with <i>a</i> = <i>b</i> = 13.949(2) Å, <i>c</i>
= 11.527(2) Å, and <i>Z</i> = 4. Compound
<b>IV</b> crystallizes in the tetragonal space group
<i>P</i>4<sub>2</sub>/<i>mnm</i> (No. 136) with <i>a</i>
= <i>b</i> = 8.5337(2) Å, <i>c</i> =
10.5595(5) Å, and <i>Z</i> = 4. Compound <b>V</b>
crystallizes in the
orthorombic space group <i>Pnma</i> (No. 62) with <i>a</i> =
15.612(2) Å, <i>b</i> = 7.0724(7) Å, <i>c</i> =
10.080(1) Å, and <i>Z</i> = 4.
Compound <b>VI</b> crystallizes in the monoclinic space group
<i>C</i>2/<i>c</i> (No. 15) with <i>a</i> =
12.9750(4) Å, <i>b</i> = 8.3282(2)
Å, <i>c</i> = 13.0568(1) Å, β = 102.940(2)°,
and <i>Z</i> = 4. Compounds <b>I</b>−<b>III</b>
contain the discrete complexes
[Pd(PQ<sub>4</sub>)<sub>2</sub>]<sup>4-</sup>
(Q = S, Se). The mixed salt <b>III</b> contains additional
noncoordinating [PSe<sub>4</sub>]<sup>3-</sup> units.
The structure of <b>IV</b> consists
of Pd(II) in square planar sulfur coordination linked by
edge-sharing [PS<sub>4</sub>]<sup>3-</sup>
tetrahedral groups to produce one-dimensional chains. The structures of <b>V</b> and<b>
VI</b> feature the
[P<sub>2</sub>Q<sub>6</sub>]<sup>4-</sup> (Q = S,
Se) group coordinated to the square
planar Pd<sup>2+</sup> atoms, yielding
[PdP<sub>2</sub>Q<sub>6</sub>]<i><sub>n</sub></i><sup>2</sup><i><sup>n</sup></i><sup>-</sup>
chains. Physical characterization was performed with DTA,
far-IR
spectroscopy, solid-state UV/vis diffuse reflectance spectroscopy, and
single-crystal optical transmission.