| 142711-13-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 142711-13-5
• 化学式: C₂₄H₂₀P*Cl₄OV
• 分子量: 548.149
• InChiKey: DQOOFMBHBWBRIK-UHFFFAOYSA-J

反应信息

• 作为产物：
  描述：

  、 氧气 、 四苯基氯化膦 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Ruhlandt-Senge, Karin; Bacher, Alfred Dirk; Koellner, Gertraude, Zeitschrift fur Naturforschung, B: Chemical Sciences, 1992, vol. 47, # 6, p. 814 - 818

  摘要：

  DOI：

文献信息

• Die Oxochlorovanadate PPh₄[VOCl₃OH], PPh₄[VOCl₄], (PPh₄ )₂ [VOCl₄ ]·2CH₃CN und (PPh₄)₂[VOCl₄]·CH₃CN mit auffälligen Abweichungen von der quadratisch-pyramidalen Anionenstruktur / The Oxochlorovanadates PPh₄[VOCl₃OH], PPh₄[VOCl₄], (PPh₄ )₂ [VOCl₄ ]·2CH₃CN and (PPh₄)₂[VOCl₄]·CH₃CN with Remarkable Deviations from the Square-Pyramidal Anion Structure
  作者：Andrea Noll、Susanne Rabe、Ulrich Müller

  DOI：10.1515/znb-1999-0504

  日期：1999.5.1

  Starting from vanadium which was not free of oxide, VCl₄ was prepared; its reaction with PPh₄Cl in the presence of K₂S₅ in dichloromethane yielded PPh₄[VOCl₃OH]. From V₂S₅, PPh₄Cl and S₂Cl₂ in acetonitrile, sulfur crystallized first, then PPh₄[VOCl₄], and then (PPh₄)₂[VOCl₄]·4CH₃CN. Upon standing with the mother liquor at -18°C, the latter was converted to (PPh₄)₂[VOCl₄]·2CH₃CN. According to its X-ray crystal structure determination, PPh₄[VOCl₃OH] (space group Pbca, a = 1105.5, b = 1920.8, c = 2242.8 pm, Z - 8) has nearly square-pyramidal anions that are associated to chains by 0-H⋯C1 bridges. PPh₄[VOCl₄] is isotypic with AsPh₄[VOCl₄] and has strictly square-pyramidal anions (space group P4/n, a = 1254.0, c = 765.0 pm, Z = 2). In (PPh₂)₂[VOCl₄]·4CH₃CN (space group P1̄, a = 1281.3, b = 1276.6, c = 1841.5 pm, α = 84.11°, β= 83.96, γ = 64.31°, Z = 2) the square pyramid of the VOCl₄ ^2- ion is distorted towards a trigonal-bipyramidal shape (C_2v symmetry) having trans-ClVCl angles of 145.88° and 156.87° and O=V-Cl angles of 107° and 101.6°. In (PPh₄)₂[VOCl₄]·2CH₃CN (space group P1, a = 1017.1, b = 1029.3, c = 2416.0, α = 77.74°, ß = 79.99°, γ = 78.94°, Z = 2), the VOCl₄ ^2- structure is even closer to trigonal-bipyramidal, with trans-ClVCl angles of 133.25° and 165.80° and 0=V-Cl angles of 113.3° and 97°.

  从含氧化物的钒开始，制备了VCl₄。在二氯甲烷中，VCl₄与PPh₄Cl在K₂S₅的存在下反应，生成PPh₄[VOCl₃OH]。在乙腈中，通过V₂S₅、PPh₄Cl和S₂Cl₂反应，首先结晶出硫，然后生成PPh₄[VOCl₄]，接着生成(PPh₄)₂[VOCl₄]·4CH₃CN。在-18°C下与母液放置后，后者转化为(PPh₄)₂[VOCl₄]·2CH₃CN。根据其X射线晶体结构测定，PPh₄[VOCl₃OH]（空间群Pbca，a = 1105.5，b = 1920.8，c = 2242.8 pm，Z = 8）具有近似方锥形的阴离子，通过0-H⋯C1桥与链相互关联。PPh₄[VOCl₄]与AsPh₄[VOCl₄]同晶（空间群P4/n，a = 1254.0，c = 765.0 pm，Z = 2），具有严格的方锥形阴离子。在(PPh₂)₂[VOCl₄]·4CH₃CN中（空间群P1̄，a = 1281.3，b = 1276.6，c = 1841.5 pm，α = 84.11°，β= 83.96，γ = 64.31°，Z = 2），VOCl₄ ^2-离子的方锥体朝向三角双锥形状（C_2v对称性），具有145.88°和156.87°的反式ClVCl角度和107°和101.6°的O=V-Cl角度。在(PPh₄)₂[VOCl₄]·2CH₃CN中（空间群P1，a = 1017.1，b = 1029.3，c = 2416.0，α = 77.74°，ß = 79.99°，γ = 78.94°，Z = 2），VOCl₄ ^2-结构甚至更接近三角双锥形，具有133.25°和165.80°的反式ClVCl角度和113.3°和97°的0=V-Cl角度。