[Pt2(dithiopropanato)4I2] | 381223-00-3

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: [Pt2(dithiopropanato)4I2]
• CAS: 381223-00-3
• 化学式: C₁₂H₂₀I₂Pt₂S₈
• 分子量: 1064.79
• InChiKey: DPQMLQRYSQDHKV-UHFFFAOYSA-H

计算性质

• 辛醇/水分配系数(LogP)：
  -0.91
• 重原子数：
  24.0
• 可旋转键数：
  4.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  [Pt2(dithiopropanato)4] 、 [Pt2(dithiopropanato)4I2] 以 甲苯 为溶剂， 以89%的产率得到[Pt2(dithiopropanato)4I]x
  参考文献：
  名称：

  Metallic Behavior and Periodical Valence Ordering in a MMX Chain Compound, Pt₂(EtCS₂)₄I

  摘要：

  A new one-dimensional (I-D) halogen-bridged mixed-valence diplatinum(II,III) compound, Pt-2(EtCS2)(4)I (3). has been successfully synthesized from [Pt-2(EtCS2)(4)] (1) and [Pt-2(EtCS2)(4)I-2] (2). These three compounds have been examined using UV-visible-near-IR, IR, polarized Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and X-ray crystal structure analyses (except for 1). Compound 3 was further characterized through electrical transport measurements, determination of the temperature dependence of lattice parameters, X-ray diffuse scattering, and SQUID magnetometry. 3 crystallizes in the monoclinic space group C2/c and exhibits a crystal structure consisting of neutral 1-D chains with a repeating -Pt-Pt-I- unit lying on the crystallographic 2-fold axis parallel to the b axis. The Pt-Pt distance at 293 K is 2.684 (1) Angstrom in the dinuclear unit, while the Pt-I distances are essentially equal (2.982 (1) and 2.978 (1) Angstrom). 3 shows relatively high electrical conductivity (5 -30 S cm(-1)) at room temperature and undergoes a metal-semiconductor transition at TM-S = 205 K. The XPS spectrum in the metallic state reveals a Pt2+ and Pt3+ mixed-valence state on the time scale of XPS spectroscopy (similar to 10(-17) S). In accordance with the metal-semiconductor transition, anomalies are observed in the temperature dependence of the crystal structure, lattice parameters, X-ray diffuse scattering, and polarized Raman spectra near TM-S. In variable-temperature crystal structure analyses, a sudden and drastic increase in the Pt-I distance near the transition temperature is observed. Furthermore, a steep increase in U-22 of iodine atoms in the I-D chain direction has been observed. The lattice parameters exhibit significant temperature dependence with drastic change in slope at about 205-240 K. This was especially evident in the unit cell parameter b (I-D chain direction) as it was found to lengthen rapidly with increasing temperature. X-ray diffraction photographs taken utilizing the fixed-film and fixed-crystal method for the metallic state revealed the presence of diffuse scattering with line shapes parallel to the a* axis indexed as (-, n + 0.5, 1) (n; integer). Diffuse scattering with k = n + 0.5 is considered to originate from the 2-fold periodical ordering corresponding to -Pt2+-Pt2+-I-Pt3+-Pt3+-I-or-Pt2+-Pt3+-I-Pt3+-Pt2+-I- in an extremely short time scale. Diffuse lines corresponding to 2-D ordering progressively decrease in intensity below 252 K and are converted to the diffuse planes corresponding to I-D ordering near TM-S. Furthermore, diffuse planes condensed into superlattice reflections below TM-S. Polarized Raman spectra show temperature dependence through a drastic low-energy shift of the Pt-I stretching mode and also through broadening of bands above TM-S.

  DOI：

  10.1021/ja010900v
• 作为产物：
  描述：

  [Pt2(dithiopropanato)4] 、 碘 以 甲苯 为溶剂， 以84%的产率得到[Pt2(dithiopropanato)4I2]
  参考文献：
  名称：

  Metallic Behavior and Periodical Valence Ordering in a MMX Chain Compound, Pt₂(EtCS₂)₄I

  摘要：

  A new one-dimensional (I-D) halogen-bridged mixed-valence diplatinum(II,III) compound, Pt-2(EtCS2)(4)I (3). has been successfully synthesized from [Pt-2(EtCS2)(4)] (1) and [Pt-2(EtCS2)(4)I-2] (2). These three compounds have been examined using UV-visible-near-IR, IR, polarized Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and X-ray crystal structure analyses (except for 1). Compound 3 was further characterized through electrical transport measurements, determination of the temperature dependence of lattice parameters, X-ray diffuse scattering, and SQUID magnetometry. 3 crystallizes in the monoclinic space group C2/c and exhibits a crystal structure consisting of neutral 1-D chains with a repeating -Pt-Pt-I- unit lying on the crystallographic 2-fold axis parallel to the b axis. The Pt-Pt distance at 293 K is 2.684 (1) Angstrom in the dinuclear unit, while the Pt-I distances are essentially equal (2.982 (1) and 2.978 (1) Angstrom). 3 shows relatively high electrical conductivity (5 -30 S cm(-1)) at room temperature and undergoes a metal-semiconductor transition at TM-S = 205 K. The XPS spectrum in the metallic state reveals a Pt2+ and Pt3+ mixed-valence state on the time scale of XPS spectroscopy (similar to 10(-17) S). In accordance with the metal-semiconductor transition, anomalies are observed in the temperature dependence of the crystal structure, lattice parameters, X-ray diffuse scattering, and polarized Raman spectra near TM-S. In variable-temperature crystal structure analyses, a sudden and drastic increase in the Pt-I distance near the transition temperature is observed. Furthermore, a steep increase in U-22 of iodine atoms in the I-D chain direction has been observed. The lattice parameters exhibit significant temperature dependence with drastic change in slope at about 205-240 K. This was especially evident in the unit cell parameter b (I-D chain direction) as it was found to lengthen rapidly with increasing temperature. X-ray diffraction photographs taken utilizing the fixed-film and fixed-crystal method for the metallic state revealed the presence of diffuse scattering with line shapes parallel to the a* axis indexed as (-, n + 0.5, 1) (n; integer). Diffuse scattering with k = n + 0.5 is considered to originate from the 2-fold periodical ordering corresponding to -Pt2+-Pt2+-I-Pt3+-Pt3+-I-or-Pt2+-Pt3+-I-Pt3+-Pt2+-I- in an extremely short time scale. Diffuse lines corresponding to 2-D ordering progressively decrease in intensity below 252 K and are converted to the diffuse planes corresponding to I-D ordering near TM-S. Furthermore, diffuse planes condensed into superlattice reflections below TM-S. Polarized Raman spectra show temperature dependence through a drastic low-energy shift of the Pt-I stretching mode and also through broadening of bands above TM-S.

  DOI：

  10.1021/ja010900v

文献信息

• ¹²⁹I Mössbauer Spectroscopic Study of a Metallic MMX Chain System
  作者：Atsushi Kobayashi、Shinji Kitao、Makoto Seto、Ryuichi Ikeda、Hiroshi Kitagawa

  DOI：10.1021/ic9007558

  日期：2009.8.17

  the charge-ordering state is in an alternate-charge-polarization phase (ACP: ···[Pt2+−Pt3+]−I0.4−−[Pt3+−Pt2+]···I0.3−···), which is consistent with a previous low-temperature X-ray diffraction study. The estimated valence states of the bridging iodines of [(C2H5)2NH2]4[Pt2(pop)4I] (pop = H2P2O52−), with a charge-polarization phase (CP: ···[Pt2+−Pt3+]−I0.4−···[Pt2+−Pt3+]−I0.4−···), and [H3N(CH2)6NH3]2[Pt2(pop)4I]

  用129 IMössbauer光谱法研究了一维碘化物桥联的混合价双核铂络合物（所谓的“ MMX链”）及其PT（III）二聚体前体。光谱由两组八胞胎在低温下，观察到的中性MMX链复合物，铂2（DTP）4 I（DTP = C 2 H ^ 5 CS 2 - ），其中在所述的PT二聚体各种电荷有序状态，表明该电荷有序状态是在可替换的电荷偏振相位（ACP：... [PT 2+ -PT 3+ ] -I 0.4〜 - [铂3+ -PT 2+ ]···我0.3-···），与先前的低温X射线衍射研究一致。[（C 2 H 5）2 NH 2 ] 4 [PT 2（pop）4 I]（pop = H 2 P 2 O 5 2-）的桥接碘的估计价态（电荷极化阶段为（ CP：·· [PT 2+ -PT 3+ ] -I 0.4- ···[PT 2+ -PT 3+ ] -I 0.4- ···），[H 3 N（CH 2）6 NH