熔融碱金属多硫属磷酸盐熔剂中的钯化学。K(4)Pd(PS(4))(2)、Cs(4)Pd(PSe(4))(2)、Cs(10)Pd(PSe(4))(4)、KPdPS(4)、K(2)PdP(2)S(6)和Cs(2)PdP(2)Se(6)的合成与表征

Palladium Chemistry in Molten Alkali Metal Polychalcophosphate Fluxes. Synthesis and Characterization of K(4)Pd(PS(4))(2), Cs(4)Pd(PSe(4))(2), Cs(10)Pd(PSe(4))(4), KPdPS(4), K(2)PdP(2)S(6), and Cs(2)PdP(2)Se(6).

作者信息

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

机构信息

Institut des Matériaux de Nantes, B.P. 32229, 44322 Nantes Cedex 03, France.

出版信息

Inorg Chem. 1997 Dec 3;36(25):5859-5868. doi: 10.1021/ic970593n.

DOI:10.1021/ic970593n

PMID:11670209

Abstract

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.

摘要

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。