[Cp2Zr(C6F5)(THF)][B(C6F5)4] | 775322-87-7

• 英文名称: [Cp2Zr(C6F5)(THF)][B(C6F5)4]
• CAS: 775322-87-7
• 化学式: C₂₀H₁₈F₅OZr*C₂₄BF₂₀
• 分子量: 1139.62
• InChiKey: HCLIAHAVFJYVJJ-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

• 作为产物：
  描述：

  四氢呋喃 、 [Cp2Zr(C6F5)(propargyltrimethylsilane)][B(C6F5)4] 以 not given 为溶剂， 以100%的产率得到[Cp2Zr(C6F5)(THF)][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 Alkene and Alkyne Complexes of d⁰ Zirconocene Pentafluorophenyl Cations
  作者：Edward J. Stoebenau、Richard F. Jordan

  DOI：10.1021/ja057524p

  日期：2006.7.1

  This paper describes the generation and properties of nonchelated d(0) zirconocene-aryl-alkene and alkyne adducts that are stabilized by the presence of beta-SiMe3 substituents on the substrates and the weak nucleophilicity of the -C6F5 ligand. The cationic complexes [(C5H4R)(2)Zr(C6F5)][B(C6F5)(4)] (4a: R) H, 4b: R) Me) were generated by methide abstraction from (C5H4R)(2)Zr(C6F5) Me by Ph3C+. NMR studies show that 4a,b contain an o-CF center dot center dot center dot Zr dative interaction and probably coordinate a PhCl molecule in PhCl solution. Addition of allyltrimethylsilane (ATMS) to 4a, b in C6D5Cl solution at low temperature produces an equilibrium mixture of (C5H4R)(2)Zr(C6F5)(H2CdCHCH2SiMe3)(+) (7a, b), 4a, b, and free ATMS. Similarly, addition of propargyltrimethylsilane (PTMS) to 4a produces an equilibrium mixture of Cp2Zr(C6F5)( HCtCCH(2)SiMe(3))(+) (8a), 4a, and free PTMS. The NMR data for 7a, b, and 8a are consistent with highly unsymmetrical substrate coordination and substantial polarization of the substrate multiple bond with significant positive charge buildup at C-int and negative charge buildup at C-term. PTMS binds to 4a more strongly than ATMS does. The ATMS adducts undergo nondissociative alkene face exchange ("alkene flipping"), i. e., exchange of the (C5H4R)(2)Zr(C6F5)(+) unit between the two alkene enantiofaces without decomplexation of the alkene, on the NMR time scale.