iPrCW(OtBu)3 | 98268-75-8

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: iPrCW(OtBu)3
• CAS: 98268-75-8
• 化学式: C₁₆H₃₄O₃W
• 分子量: 458.294
• InChiKey: HKRBNZVHCDFWDJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.95
• 重原子数：
  20.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  27.69
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  iPrCW(OtBu)3 在 苯甲酸 作用下， 以 乙醚 为溶剂， 以80%的产率得到W(CH₂C(CH₃)2)(OC(CH₃)3)2(O₂CC₆H₅)2
  参考文献：
  名称：

  Freudenberger, John H.; Schrock, Richard R., Organometallics, 1985, vol. 4, # 11, p. 1937 - 1944

  摘要：

  DOI：
• 作为产物：
  描述：

  异丁腈 、 ditungsten hexakis(tert-butoxide) 以 正戊烷 为溶剂， 以89%的产率得到iPrCW(OtBu)3
  参考文献：
  名称：

  Freudenberger, John H.; Schrock, Richard R., Organometallics, 1985, vol. 4, # 11, p. 1937 - 1944

  摘要：

  DOI：

文献信息

• Metathesis of Nitrogen Atoms within Triple Bonds Involving Carbon, Tungsten, and Molybdenum
  作者：Beth A. Burroughs、Bruce E. Bursten、Shentan Chen、Malcolm H. Chisholm、Andy R. Kidwell

  DOI：10.1021/ic8003917

  日期：2008.6.1

  ((BuO)-O-t)(3)Mo N and W-2(OBut)(6)(M M) react in hydrocarbons to form Mo-2(OBut)(6)(M M) and ((BuO)-O-t)(3)W N via the reactive intermediate MoW(OBut)(6)(M M). ((BuO)-O-t)(3)W N and CH3C N-15 react in tetrahydrofuran (THF) at room temperature to give an equilibrium mixture involving ((BuO)-O-t)(3)W N-15 and CH3C N. The ((BuO)-O-t)(3)W N compound is similarly shown to act as a catalyst for N-15-atom scrambling between MeC13 N-15 and PhC N to give a mixture of MeC13 N and PhC N-15. From studies of degenerate scrambling of IN atoms involving ((BuO)-O-t)(3)W N and MeC13 N in THF-d(8) by C-13H-1} NMR spectroscopy, the reaction was found to be first order in acetonitrile and the activation parameters were estimated to be Delta H-not equal = 13.4(7) kcal/mol and Delta S-not equal = -32(2) eu. A similar reaction is observed for ((BuO)-O-t)(3)Mo N and (CH3CN15)-N-not equal upon heating in THF-d(8). The reaction is suppressed in pyridine solutions and not observed for the dimeric [((BuMe2SiO)-Me-t)(3)W N](2). The reaction pathway has been investigated by calculations employing density functional theory on the model compounds (MeO)(3)M N and CH3C N where M = Mo and W. The transition state was found to involve a product of the 2 + 2 cycloaddition of M N and C N, a planar metalladiazacyclobutadiene. This resembles the pathway calculated for alkyne metathesis involving (MeO)(3)W CMe, which modeled the metathesis of ((BuO)-O-t)(3)W CBut. The calculations also predict that the energy of the transition state is notably higher for M = Mo relative to M = W.

  ((BuO)-O-t)(3)Mo N 和 W-2(OBut)(6)(M M) 在烃类中反应，通过反应中间体 MoW(OBut)(6)(M M) 形成 Mo-2(OBut)(6)(M M) 和 ((BuO)-O-t)(3)W N。((BuO)-O-t)(3)W N 和 CH3C N-15 在四氢呋喃 (THF) 中于室温下反应，生成 ((BuO)-O-t)(3)W N-15 和 CH3C N 的平衡混合物。((BuO)-O-t)(3)W N 化合物还表现出催化 N-15 原子在 MeC13 N-15 和 PhC N 间重排的能力，生成 MeC13 N 和 PhC N-15 的混合物。通过 C-13H-1} 核磁共振光谱对涉及 ((BuO)-O-t)(3)W N 和 MeC13 N 在 THF-d(8) 中的 IN 原子退化重排研究发现，反应对丙腈呈一级反应，活化参数估计为 ΔH≠ = 13.4(7) kcal/mol 和 ΔS≠ = -32(2) eu。类似地，((BuO)-O-t)(3)Mo N 和 (CH3CN15)-N≠ 在 THF-d(8) 中加热时也观察到类似反应。该反应在吡啶溶液中受到抑制，且未在二聚体 [((BuMe2SiO)-Me-t)(3)W N]₂ 中观察到。通过密度泛函理论对模型化合物 (MeO)(3)M N 和 CH3C N（M = Mo 和 W）进行计算，研究了反应路径。发现过渡态涉及 M N 和 C N 的 2 + 2 环加成产物，即平面金属杂环丁二烯。此路径与对含 (MeO)(3)W CMe 的炔烃复分解反应的计算结果相似，其中 (MeO)(3)W CMe 模拟了 ((BuO)-O-t)(3)W CBut 的复分解反应。计算还预测，M = Mo 时的过渡态能量显著高于 M = W 时的能量。
• Asymmetric alkylidene and oxo complexes of tungsten(VI)
  作者：Joseph A. Heppert、Steven D. Dietz、Nancy W. Eilerts、Robert W. Henning、Martha D. Morton、Fusao Takusagawa、Frank A. Kaul

  DOI：10.1021/om00031a029

  日期：1993.7

  Reactions between (t-BuO)3W(=CR) derivatives and 1,1'-bi-2-naphthols (H2R2BINO, R = Me,Br,Ph) generate mononuclear C1-symmetric (R2BINO)(t-BuO)2W(=CHR) complexes. An analogous reaction with 2 equiv of H2Me2BINO generates (Me2BINO)2W(=CHPh), while a reaction between H2Me2BINO and (t-BuO)4W(=O) produces (Me2BINO)(t-BuO)2W(=O). This oxo complex was characterized by X-ray crystallography, which shows it to be a highly-distorted trigonal bipyramidal complex in which the Me2BINO ligand adopts a lambda chelate stereochemistry. Although the complexes show little stereoselectivity in Wittig-like alkylidene transfer to benzaldehyde, the ring opening metathesis polymerization of norbornene proceeds with modest stereoselectivity. The fraction of cis-polynorbornene increases in concert with the steric demands of the substituents on the R2BINO ligand. Crystal data for (Me2BINO)(t-BuO)2W(=O) at 113 K: a = 11.426(3) angstrom, b = 14.733(3) angstrom, c = 16.716(4) angstrom, beta = 105.87(2)degrees, Z = 4, D(calc.) = 1.616, space group P2(1)/n (No. 14), R(F) = 0.053, R(w)(F) = 0.106 for 3451 reflections (F(o) > 0).