[Cp'Zr(O(t)Bu)(HCCMe)][B(C6F5)4] | 512163-96-1

• 英文名称: [Cp'Zr(O(t)Bu)(HCCMe)][B(C6F5)4]
• CAS: 512163-96-1
• 化学式: C₁₉H₂₇OZr*C₂₄BF₂₀
• 分子量: 1041.69
• InChiKey: ALERCWAIGJTLGH-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：

  [(C5H4Me)2Zr(O(t)Bu)(ClCD2Cl)][B(C6F5)4] 、 丙炔 以 二氯甲烷-D2 为溶剂， 生成 [Cp'Zr(O(t)Bu)(HCCMe)][B(C6F5)4]
  参考文献：
  名称：

  Alkyne and Alkene Complexes of a d⁰ Zirconocene Aryl Cation

  摘要：

  The generation and properties of nonchelated Zr-aryl-alkyne and Zr-aryl-alkene complexes that are stabilized by the presence of beta-Si-substituents in the alkyne and alkene ligands and fluorination of the aryl ligand are described. Reaction of [Cp'2Zr(OtBu)(ClCD2Cl)][B(C6F5)4] (1, Cp' = C5H4Me) with alkyne and alkene substrates (L) generates Cp'2Zr(OtBu)(L)+ adducts (L = HCCCH2SiMe3 (2); H2C=CHCH2SiMe3 (3); HCCMe (4); H2C=CHCH2CMe3 (5)). Equilibrium constants for substrate binding (Keq = [Zr-L][1]-1[L]-1; CD2Cl2, -89 degrees C) are much larger for the beta-Si-substituted compounds 2 (1.0(2) x 105 M-1) and 3 (1.7(4) x 103 M-1) than for hydrocarbon analogues 4 (3.6(7) x 102 M-1) and 5 (1.9(1) M-1), which is ascribed to beta-Si stabilization of the partial positive charge on Cint of the bound substrate. [Cp2Zr(C6F5)][B(C6F5)4] (7, Cp = C5H5) was generated by the reaction of Cp2Zr(C6F5)Me with [Ph3C][B(C6F5)4] in C6D5Cl. Reaction of 7 with alkyne and alkene substrates (L) generates Cp2Zr(C6F5)(L)+ adducts (L = HCCCH2SiMe3 (8); H2C=CHCH2SiMe3 (10)). No insertion of the substrate into the Zr-C6F5 bond is observed in 8 (at -38 degrees C) or 10 (up to 22 degrees C). The allyltrimethylsilane ligand in 10 undergoes nondissociative alkene face exchange ("alkene flipping", i.e., exchange of the Cp2Zr(C6F5)+ unit between the two alkene enantiofaces without alkene dissociation), with a first-order rate constant kflip = 23(1) s-1 (C6D5Cl, -38 degrees C). 10 also undergoes slower reversible decomplexation of the alkene (kdissoc = 5.0(8) s-1; C6D5Cl, -38 degrees C).

  DOI：

  10.1021/ja045794m

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.