W(CO)5(triphenylbismuthine) | 32356-10-8

• 英文名称: W(CO)5(triphenylbismuthine)
• CAS: 32356-10-8
• 化学式: C₂₃H₁₅BiO₅W
• 分子量: 764.199
• InChiKey: YNEHOOFSHUYCRK-UHFFFAOYSA-N

计算性质

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

• 作为产物：
  描述：

  pentacarbonyl(η2-bis(trimethylsilyl)ethyne)tungsten(0) 、 三苯基铋 以 环己烷 为溶剂， 生成 W(CO)5(triphenylbismuthine)
  参考文献：
  名称：

  Substitution kinetics of W(CO)5(η2-bis(trimethylsilyl)ethyne) with triphenylbismuthine

  摘要：

  The labile complex W(CO)(5)(eta(2)-btmse) undergoes replacement of bis(trimethylsilyl)ethyne, btmse, by triphenylbismuthine in cyclohexane solution at an observable rate in the temperature range of 35-50 degrees C yielding almost solely W(CO)(5)(BiPh3) as the final product. The kinetics of this substitution reaction was studied in cyclohexane solution by quantitative FT-IR spectroscopy. The substitution reaction obeys a pseudo-first-order kinetics with respect to the concentration of the starting complex. The observed rate constant, k(obs), was determined at four different temperatures and three different concentrations of the entering ligand BiPh3 in the range 16.8-65.4 mM. From the evaluation of kinetic data a possible reaction mechanism was proposed in which the rate determining step is the cleavage of metal-alkyne bond in the complex W(CO)(5)(eta(2)-btmse). A rate law was derived from the proposed mechanism. From the dependence of kobs on the entering ligand concentration, the rate constant k(1) for the rate determining step was estimated at all temperatures. The activation enthalpy (106 +/- 2 kJ mol(-1)) and the activation entropy (111 +/- 6 J K-1 mol(-1)) were determined for this rate determining step from the evaluation of k(1) values at different temperatures. The large positive value of the activation entropy is consistent with the dissociative nature of reaction. The large value of the activation enthalpy, close to the calculated tungsten-alkyne bond dissociation energy, also supports this dissociative rate-determining step of the substitution reaction. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2006.03.036

文献信息

• Triphenylbismuthine complexes of group 6 metal carbonyls: X-ray crystal structures of [M(CO)5(BiPh3)] (M = Mo or W)
  作者：Nicholas J. Holmes、William Levason、Michael Webster

  DOI：10.1016/s0022-328x(97)00236-2

  日期：1997.1

  tetrahydrofuran), and characterised by analysis, FAB mass spectrometry, IR and 13C(1H)-NMR spectroscopy, and the results compared with literature data on [M(CO)5(EPh3)] (E = P, As or Sb). The crystal structures of the Mo and W species have been determined (Mo-Bi 2.832(1), W-Bi 2.829(1) Å).

  [M（CO）5（BiPh 3）]（M = Cr，Mo或W）配合物是由thf（thf =四氢呋喃）中的[M（CO）5（thf）]和BiPh 3制备的，其特征在于分析，FAB质谱，IR和13 C（1 H）-NMR光谱，并将结果与​​[M（CO）5（EPh 3）]（E = P，As或Sb）的文献数据进行比较。已经确定了Mo和W物种的晶体结构（Mo-Bi 2.832（1），W-Bi 2.829（1）Å）。
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Bi: Org.Verb., 1.3.3.2.4.3, page 72 - 78
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• Octahedral metal carbonyls—XVIII triphenylbismuth derivatives of the group VIB metal carbonyls
  作者：Richard A. Brown、Gerard R. Dobson

  DOI：10.1016/0022-1902(71)80496-7

  日期：1971.3
• Brown, R. A.; Dobson, G. R., Inorganica Chimica Acta, 1972, vol. 6, p. 1965 - 1971
  作者：Brown, R. A.、Dobson, G. R.

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• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Bi: Org.Verb., 3.2.2.2, page 147 - 150
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