Chondroudis Konstantinos, Kanatzidis Mercouri G., Sayettat Julien, Jobic Stéphane, Brec Raymond
Institut des Matériaux de Nantes, B.P. 32229, 44322 Nantes Cedex 03, France.
Inorg Chem. 1997 Dec 3;36(25):5859-5868. doi: 10.1021/ic970593n.
The reaction of Pd with a molten mixture of A(2)Q(x)()/P(2)Q(5)/Q (A = K, Q = S, x = 3; A = Cs, Q = Se, x = 1) produced the molecular compounds K(4)Pd(PS(4))(2) (I), Cs(4)Pd(PSe(4))(2) (II), and Cs(10)Pd(PSe(4))(4) (III) and the solid-state KPdPS(4) (IV), K(2)PdP(2)S(6) (V), and Cs(2)PdP(2)Se(6) (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 P&onemacr; (No. 2) with a = 6.380(1) Å, b = 6.897(1) Å, c = 8.999(1) Å, alpha = 87.777(8) degrees, beta = 81.581(8) degrees, gamma = 84.429(9) degrees, and Z = 1. Compound II crystallizes in the monoclinic space group P2(1)/c (No. 14) with a = 7.491(2) Å, b = 13.340(2) Å, c = 10.030(3) Å, beta = 92.21(2) degrees, and Z = 2. Compound III crystallizes in the tetragonal space group P&fourmacr;2c (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 P4(2)/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, beta = 102.940(2) degrees, and Z = 4. Compounds I-III contain the discrete complexes Pd(PQ(4))(2)(-) (Q = S, Se). The mixed salt III contains additional noncoordinating PSe(4)(-) units. The structure of IV consists of Pd(II) in square planar sulfur coordination linked by edge-sharing PS(4)(-) tetrahedral groups to produce one-dimensional chains. The structures of V andVI feature the P(2)Q(6)(-) (Q = S, Se) group coordinated to the square planar Pd(2+) atoms, yielding PdP(2)Q(6)()(2)(n)()(-) chains. Physical characterization was performed with DTA, far-IR spectroscopy, solid-state UV/vis diffuse reflectance spectroscopy, and single-crystal optical transmission.
钯与A₂Qₓ/P₂Q₅/Q的熔融混合物（A = K，Q = S，x = 3；A = Cs，Q = Se，x = 1）反应生成了分子化合物K₄Pd(PS₄)₂（I）、Cs₄Pd(PSe₄)₂（II）和Cs₁₀Pd(PSe₄)₄（III）以及固态的KPdPS₄（IV）、K₂PdP₂S₆（V）和Cs₂PdP₂Se₆（VI）。化合物I - III对空气和水敏感，而IV - VI对空气和水稳定。除了VI为黑色外，所有晶体均为红色或深红色。它们均呈棒状。化合物I结晶于三斜空间群P&onemacr;（编号2），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)°，Z = 1。化合物II结晶于单斜空间群P2₁/c（编号14），a = 7.491(2) Å，b = 13.340(2) Å，c = 10.030(3) Å，β = 92.21(2)°，Z = 2。化合物III结晶于四方空间群P&fourmacr;2c（编号112），a = b = 13.949(2) Å，c = 11.527(2) Å，Z = 4。化合物IV结晶于四方空间群P4₂/mnm（编号136），a = b = 8.5337(2) Å，c = 10.5595(5) Å，Z = 4。化合物V结晶于正交空间群Pnma（编号62），a = 15.612(2) Å，b = 7.0724(7) Å，c = 10.080(1) Å，Z = 4。化合物VI结晶于单斜空间群C2/c（编号15），a = 12.9750(4) Å，b = 8.3282(2) Å，c = 13.0568(1) Å，β = 102.940(2)°，Z = 4。化合物I - III包含离散的配合物[Pd(PQ₄)₂]⁴⁻（Q = S，Se）。混合盐III包含额外的非配位[PSe₄]³⁻单元。IV的结构由处于平面正方形硫配位环境的Pd(II)通过边共享的[PS₄]³⁻四面体基团连接形成一维链。V和VI的结构特征是[P₂Q₆]⁴⁻（Q = S，Se）基团与平面正方形Pd²⁺原子配位，形成[PdP₂Q₆]ₙ²ₙ⁻链。通过差示热分析、远红外光谱、固态紫外/可见漫反射光谱和单晶光学透射进行了物理表征。
