trans-[(η5-C5H5)W(MeCN)2I(η2-COMe)]BF4 | 166329-77-7

• 英文名称: trans-[(η5-C5H5)W(MeCN)2I(η2-COMe)]BF4
• CAS: 166329-77-7
• 化学式: BF₄*C₁₁H₁₄IN₂OW
• 分子量: 587.804
• InChiKey: LFCXPKZAVZCWRS-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：

  [(η5-C5H5)W(MeCN)3(η2-COMe)](BF4)2 、 乙腈 、 potassium iodide 以 乙腈 为溶剂， 以90%的产率得到trans-[(η5-C5H5)W(MeCN)2I(η2-COMe)]BF4
  参考文献：
  名称：

  Halide and Tertiary Phosphine Derivatives of the Tungsten (IV) .eta.2-Acetyl Complex CpW(NCMe)3(.eta.2-COMe)2+. Reversible Ag+-Assisted Opening of an .eta.2-Acetyl Group?

  摘要：

  The dicationic W(TV) eta(2)-acetyl complex CpW(NCMe)(3)(eta(2)-COMe)(2+) (1) serves as the precursor for new tungsten(IV) eta(2)-acetyl derivatives, Treatment of 1 with halides provided trans-CpW(NCMe)(2)(X)(eta(2)-COMe)(+) (X = Cl, Br, I) in high yields. The reaction between CpW(NCMe)(2)(Br)(eta(2)-COMe)(+) and dppe yielded the 5-ring chelate CpW(eta(2)-dppe)(Br)(eta(2)-COMe)(+), while reactions with monodentate tertiary phosphines led to trans-CpW(PR(3))(2)(Br) (eta(2)-COMe)(+) via the intermediate CpW(NCMe)(PR(3))(Br) (eta(2)-COMe)(+) (PR(3) = PMePh(2), PPh(3)). Addition of acetonitrile to a nitromethane solution of CpW(PPh(3))(2)(Br)(eta(2)-COMe)(+) set up an equilibrium between the substrate and CpW(NCMe)(PPh(3))(Br)(eta(2)-COMe)(+). When AgBF4 was added, this ligand substitution reaction was accelerated. Reversible attachment of Ag+ at the 1 eta(2)-acetyl oxygen, ring opening, and reversible BF4- binding at the resulting vacant coordination site at W in trans-CpW(PMePh(2))(2)(Br)(eta(2)-COMe)(+) is suggested on the basis of H-1 and F-19 NMR spectroscopic observations. Similar steps are thought to be involved in the Ag+-catalyzed ligand substitution reaction. A single-crystal X-ray structure determination of CpW(NCMe)(2)(Br)(eta(2)-COMe)(+) revealed a four-legged piano stool structure in which the Br and eta(2)-acetyl ligands are located in a trans relationship and the C-O bond vector points away from the Cp ligand. Crystal data for 4(BF4-): space group P (1) over bar, a = 7.782(2) Angstrom, b = 12.277(3) Angstrom, c = 16.173(4) Angstrom, alpha = 89.48(2)degrees, beta = 88.81(2)degrees, and gamma = 88.74(2)degrees. Least-squares refinement based on 4849 reflections converged to R = 0.056 and R(W) = 0.054.

  DOI：

  10.1021/ic00116a010