[W2Cl4(PMe3)4] | 73133-20-7

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: [W2Cl4(PMe3)4]
• CAS: 73133-20-7；73495-54-2
• 化学式: C₁₂H₃₆Cl₄P₄W₂
• 分子量: 813.825
• InChiKey: QEONACJVCNECKN-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  8.18
• 重原子数：
  22.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  [W2Cl4(PMe3)4] 在 air 作用下， 以 二氯甲烷 为溶剂， 生成 (l3-oxidaneylidyne)tris(trimethyl-l5-phosphaneyl)tungsten(VIII) chloride
  参考文献：
  名称：

  Two New Ditungsten Species Containing Chloride and Trimethylphosphine Ligands

  摘要：

  The action of PhI . Cl-2 on W2Cl4(PMe(3))(4) in 1:1 mole ratio gives brown 1,3,6-W2Cl5(PMe(3))(3). The EPR at 10 K in frozen CH2Cl2 solution has a broad signal at g 1.83. The molecular structure was determined by X-ray crystallography and shows a W-W distance of 2.291(1) Angstrom, about 0.03 Angstrom longer than that in W2Cl4(PMe(3))(4). Crystal data: monoclinic space group C2/c with cell dimensions of a 13.423(2) Angstrom, b = 12.0768(9) Angstrom, c 28.247(5) Angstrom, beta = 93.360(7)degrees, V = 457,1(1) Angstrom(3), and Z = 8. There is a 1.8% orientational disorder. When a solution of W2Cl6(PMe(3))4 in CH2Cl2 plus hexanes was allowed to stand at -15 degrees C for several months, brown crystals of [HPMe(3)](2)[W2Cl8(PMe(3))]. CH2Cl2 were obtained. The anion is a face-sharing bioctahedron, with a W-W bond length of 2.433(1) Angstrom. Crystal data: monoclinic space group P2(1)/m with cell dimensions of a 9.398(1) Angstrom, b = 9.836(2) Angstrom, c 16.687(5) Angstrom, beta = 97.78(2)degrees, V = 1528.4(6) Angstrom(3), and Z = 2.

  DOI：

  10.1021/ic00118a031
• 作为产物：
  描述：

  WCl2(PMe3)4 以 二丁醚 为溶剂， 以60%的产率得到[W2Cl4(PMe3)4]
  参考文献：
  名称：

  Synthesis of a class of complexes containing tungsten-tungsten quadruple bonds

  摘要：

  DOI：

  10.1021/ja00524a041

文献信息

• Preparation and electronic characterization of M2(CCR)4(PMe3)4: a class of conjugated transition-metal complexes
  作者：Timothy C. Stoner、Richard F. Dallinger、Michael D. Hopkins

  DOI：10.1021/ja00170a046

  日期：1990.7

  an unsaturated organic chain should, given the widely tunable optical properties of metal complexes and the relative ease with which they support open-shell electronic configurations, significantly enhance the diverse physical properties possessed by conjugated organic molecules; dyes, conducting polymers, and carbon-based nonlinear optical materials are but a few examples of such species. Herein the

  共轭有机分子和聚合物包含广泛且基本重要的一类分子，在过渡金属化学中没有可比拟开发和明确定义的对应物。作者对共轭金属配合物的兴趣源于以下信念：考虑到金属配合物的广泛可调光学性质以及它们支持开放的相对容易，将多重键合过渡金属中心并入不饱和有机链的主链中-壳层电子构型，显着增强了共轭有机分子所具有的多种物理性质；染料、导电聚合物和碳基非线性光学材料只是此类物种的几个例子。
• Charge transfer photochemistry of quadruply bonded ditungsten halophosphine complexes
  作者：Tsui-Ling C. Hsu、Daniel S. Engebretson、Sara A. Helvoigt、Daniel G. Nocera

  DOI：10.1016/0020-1693(95)04582-1

  日期：1995.12

  transient absorption spectroscopy shows the production of the 1 δδ ∗ excited state, which decays to ground state over times commensurate with the decay of 1 δδ ∗ luminescence. In hydrocarbon solutions, no transient intermediate or photochemistry is observed, indicating that the LMCT excited state, although capable of reducing a CX bond, cannot activate the stronger CH bonds of hydrocarbons. The photochemistry

  摘要四重金属-金属键合络合物W2Cl4（PR3）4（PR3 = PMe3，PMe2Ph，PBu3）在二氯甲烷中以近紫外光激发（λ> 375 nm）进行光反应，得到W2（II，III）混合价光合产物。光解溶液的电子吸收光谱和EPR光谱与通过PhICI2对W2Cl4（PR3）4进行热氧化而获得的光谱相同，已知会产生W2Cl5（PR3）3。光解溶液的随后反应产生氧化的界面生物体W2（III，III）卤代膦。对有机光产物的分析表明，卤代烃溶剂被一个电子还原而产生氯甲基自由基。当自由基以低收率产生时，从溶剂中提取氢似乎足以与二聚反应竞争，并且仅观察到氯甲烷。然而，在较高浓度下，氯甲基基团偶合生成二氯乙烷。仅在W2Cl4（PR3）4的LMCT吸收歧管的近紫外激发下才观察到光反应。在较低的能量波长下，瞬态吸收光谱显示出1δδ*激发态的产生，该态随与1δδ*发光的衰减相应的时间衰减到基态。在烃溶液中，未观
• Schrock, Richard R.; Sturgeoff, Lynda G.; Sharp, Paul R., Inorganic Chemistry, 1983, vol. 22, # 20, p. 2801 - 2806
  作者：Schrock, Richard R.、Sturgeoff, Lynda G.、Sharp, Paul R.

  DOI：——

  日期：——
• Cotton; Eglin, Judith L.; James, Chris A., Inorganic Chemistry, 1993, vol. 32, # 5, p. 681 - 686
  作者：Cotton、Eglin, Judith L.、James, Chris A.

  DOI：——

  日期：——
• Stoner, Timothy C.; Geib, Steven J.; Hopkins, Michael D., Journal of the American Chemical Society, 1992, vol. 114, # 11, p. 4201 - 4204
  作者：Stoner, Timothy C.、Geib, Steven J.、Hopkins, Michael D.

  DOI：——

  日期：——