[(C5H4Me)2Zr(O(t)Bu)][B(C6F5)4] | 512163-89-2

• 英文名称: [(C5H4Me)2Zr(O(t)Bu)][B(C6F5)4]
• 英文别名: [Cp'2Zr(O-t-Bu)][B(C6F5)4]
• CAS: 512163-89-2
• 化学式: C₁₆H₂₃OZr*C₂₄BF₂₀
• 分子量: 1001.63
• InChiKey: SFWQHMKMULLYHC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  乙烯 、 [(C5H4Me)2Zr(O(t)Bu)][B(C6F5)4] 以 二氯甲烷-D2 为溶剂， 生成 [(C5H4Me)2Zr(O(t)Bu)(ethylene)][B(C6F5)4]
  参考文献：
  名称：

  烯烃和炔烃与阳离子 d0Zirconocene 醇盐配合物的配位

  摘要：

  本文介绍了无碱 (C5R5)2Zr(OtBu)+ 阳离子的合成、对这些阳离子的非螯合烯烃和炔烃加合物的直接观察，以及对这些新物种的热力学和动力学性质的研究。%@mt;sys@%Cp%@/xs;55;%lnwidth@%'%@/xs;63;(%lnwidth-x55)@%%@mh;-x63@%%@sb@%的反应2%@sbx@%%@/hd@%ZrMe%@sb@%2%@sbx@%%@mx@% (Cp' = C5H4Me) 与叔丁醇，然后是 [Ph3C][B(C6F5) 4] 在苯中的产率 [%@mt;sys@%Cp%@/xs;55;%lnwidth@%'%@/xs;63;(%lnwidth-x55)@%%@mh;-x63@%% @sb@%2%@sbx@%%@/hd@%Zr%@/hd@%%@fn;(;vis;full;auto@%O%@ital@%%@ex@%t%@ rsf@%%@exx@%%@/

  DOI：

  10.1021/ja029963j
• 作为产物：
  描述：

  (C5H4Me)2Zr(O(t)Bu)Me 、 三苯碳四(五氟苯基)硼酸盐 以 苯 为溶剂， 以80%的产率得到[(C5H4Me)2Zr(O(t)Bu)][B(C6F5)4]
  参考文献：
  名称：

  Nonchelated d⁰ Zirconium−Alkoxide−Alkene Complexes

  摘要：

  The reaction of Cp'Zr-2((OBu)-Bu-t)Me (Cp' = C5H4Me) and [Ph3C][B(C6F5)(4)] yields the base-free complex [Cp'Zr-2((OBu)-Bu-t)][B(C6F5)(4)] (6), which exists as Cp'Zr-2((OBu)-Bu-t)(ClR)(+) halocarbon adducts in CD2Cl2 or C6D5Cl solution. Addition of alkenes to 6 in CD2Cl2 solution at low temperature gives equilibrium mixtures of Cp'(2) -Zr((OBu)-Bu-t)(alkene)(+) (12a-I), 6, and free alkene. The NMR data for 12a-I are consistent with unsymmetrical alkene bonding and polarization of the alkene C = C bond with positive charge buildup at C-int and negative charge buildup at C-term. These features arise due to the lack of d-pi(*) back-bonding. Equilibrium constants for alkene coordination to 6 in CD2Cl2 at -89 degrees C, K-eq = [12][6](-1)[alkene](-1), vary in the order: vinylferrocene (4800 M-1) >> ethylene (7.0) approximate to alpha-olefins > cis-2-butene (2.2) > trans-2-butene (< 0.1). Alkene coordination is inhibited by sterically bulky substituents on the alkene but is greatly enhanced by electron-donating groups and the beta-Si effect. Compounds 12a-I undergo two dynamic processes: reversible alkene decomplexation via associative substitution of a CD2Cl2 molecule, and rapid rotation of the alkene around the metal-(alkene centroid) axis.

  DOI：

  10.1021/ja0575225

文献信息

• Nonchelated Zr^IV−Alkoxide−Alkyne Complexes
  作者：Edward J. Stoebenau、Richard F. Jordan

  DOI：10.1021/om050947f

  日期：2006.7.1

  Addition of alkynes to [Cp'Zr-2((OBu)-Bu-t)][B(C6F5)(4)] (Cp' = C5H4Me, 2) at low temperature in CD2Cl2 solution yields equilibrium mixtures of Cp'2Zr((OBu)-Bu-t)(RC=CR')(+) (3a-g), 2, and free alkyne. The C-13 NMR C-int resonance of terminal alkynes shifts far downfield upon coordination, while the C-term resonance shifts upfield, consistent with polarization of the C=C bond with partial positive charge on C-int and partial negative charge on C-term, probably due to unsymmetrical coordination. Alkynes bind more strongly to 2 than do similar alkenes, but are readily displaced by Lewis bases such as THF. Increasing the steric bulk of the alkyne decreases the coordination strength. Propargyltrimethylsilane coordinates particularly strongly, due to beta-Si stabilization of the positive charge on C-int of the coordinated alkyne. Compounds 3a- g undergo two dynamic processes: reversible alkyne decomplexation and rotation around the metal( alkyne centroid) axis.