decamethylvanadocene*BPh4 | 869648-36-2

• 英文名称: decamethylvanadocene*BPh4
• 英文别名: [(Cp*)2V]BPh4
• CAS: 869648-36-2
• 化学式: C₂₀H₃₀V*C₂₄H₂₀B
• 分子量: 640.634
• InChiKey: PFYDVQZNIPUBKS-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：
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• 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：

  decamethylvanadocene*BPh4 、 N,N-二甲基苯铵四(五氟苯基)硼酸盐 以 氟苯 为溶剂， 以89%的产率得到[(η5-C5Me5)2V][B(C6F5)4]
  参考文献：
  名称：

  裸 (C5Me5)2M 阳离子（M = Sc、Ti 和 V）及其氟芳烃配合物

  摘要：

  合成了三价 3d 金属 Sc、Ti 和 V 的离子茂金属配合物 [Cp*(2)M][BPh(4)](Cp* = C(5)Me(5)) 并在结构上进行了表征。对于 M = Sc，阴离子通过苯基之一与金属中心弱相互作用，但对于 M = Ti 和 V，阳离子是裸露的。它们每个都包含一个强烈扭曲的 Cp* 配体，具有一个 (V) 或两个 (Ti) 激动性 CH...M 相互作用，涉及 Cp*Me 基团。对于 Sc 和 Ti，这些路易斯酸性物质与氟苯和 1,2-二氟苯反应生成 [Cp*(2)M(kappaF-FC(6)H(5))(n)][BPh(4)] ( M = Sc, n = 2; M = Ti, n = 1) 和 [Cp*(2)M(kappa(2)F-1,2-F(2)C(6)H(4))][ BPh(4)]，过渡金属的 kappaF-氟苯和 kappa(2)F-1,2-二氟苯加合物的第一个例子。使用全氟阴离子

  DOI：

  10.1021/ja054544i
• 作为产物：
  描述：

  bis(pentamethylcyclopentadienyl)methylvanadium(III) 、 N,N-dimethylanilinium tetraphenylborate 以 甲苯 为溶剂， 以71%的产率得到decamethylvanadocene*BPh4
  参考文献：
  名称：

  裸 (C5Me5)2M 阳离子（M = Sc、Ti 和 V）及其氟芳烃配合物

  摘要：

  合成了三价 3d 金属 Sc、Ti 和 V 的离子茂金属配合物 [Cp*(2)M][BPh(4)](Cp* = C(5)Me(5)) 并在结构上进行了表征。对于 M = Sc，阴离子通过苯基之一与金属中心弱相互作用，但对于 M = Ti 和 V，阳离子是裸露的。它们每个都包含一个强烈扭曲的 Cp* 配体，具有一个 (V) 或两个 (Ti) 激动性 CH...M 相互作用，涉及 Cp*Me 基团。对于 Sc 和 Ti，这些路易斯酸性物质与氟苯和 1,2-二氟苯反应生成 [Cp*(2)M(kappaF-FC(6)H(5))(n)][BPh(4)] ( M = Sc, n = 2; M = Ti, n = 1) 和 [Cp*(2)M(kappa(2)F-1,2-F(2)C(6)H(4))][ BPh(4)]，过渡金属的 kappaF-氟苯和 kappa(2)F-1,2-二氟苯加合物的第一个例子。使用全氟阴离子

  DOI：

  10.1021/ja054544i

文献信息

• Reactivity of cationic decamethylmetallocene complexes towards ketones
  作者：Marco W. Bouwkamp、Peter H.M. Budzelaar、Auke Meetsma、Bart Hessen

  DOI：10.1016/j.jorganchem.2011.02.023

  日期：2011.5

  Reaction of decamethylmetallocene cations [Cp-2*M](+) (M = Sc, Ti, V) with acetone and benzophenone resulted in the formation of the corresponding acetone adducts [Cp-2*M(OCMe2)(n)](+) (M = Sc, n = 2; M = Ti, n = 1; M = V, n = 1) and benzophenone adducts [Cp-2*M(OCPh)](+). The stoichiometry of these adducts is determined by both the electronic configuration of the metal center as well as steric pressure imparted by the large Cp*-ligands. In addition, the M-O-C angle is controlled by the number of free valence orbitals of the Cp-2*M unit. (C) 2011 Elsevier B.V. All rights reserved.
• Bridging Azines in the Coordination Sphere of Low-Valent Vanadocene Derivatives
  作者：Markus Jordan、Wolfgang Saak、Detlev Haase、Rüdiger Beckhaus

  DOI：10.1021/om100612e

  日期：2010.11.22

  Complexes of vanadocene(II) and -(III) derivatives with aromatic N-heterocyclic ligands are scarcely known. Here we present the first syntheses of several mono-, di-, and trinuclear complexes of this type and their detailed characterization. Reactions of vanadocene(II) derivatives are limited to N-heterocycles with distinct pi-acceptor ability such as 4,4'-azobis(pyridine), which reacts as a bridging ligand to form [(Cp2V)(2)(mu(2)-Py2N2)] (13). In contrast Cp2VII reacts with, for example, 1,2-bis(4-pyridiyl)acetylene (C2Py2) solely to give the corresponding metallacyclopropene [Cp2V(eta(2)-C2Py2)] (12) without affecting the pyridyl moieties. On the other hand, the reactivity of vanadocene(III) cations with this class of ligands is unrestricted and dominated by the acid-base properties of the reactants. The application of permethylated cyclopentadienyl ligands (Cp*) significantly enhances the solubility of those complexes, which leads to a better crystallizability. Due to the cationic properties of vanadocenium(III) derivatives, reactions with the smallest aromatic bridging N-heterocycle, pyrazine, afforded the rarely known mononuclear pyrazine complexes [Cp-2'V(Pz)][BPh4] (Cp' = Cp (17), Cp* (20); Pz = C4H4N2), whereas other N-heterocycles with expanded pi-systems such as 4,4'-bipyridine (4-Bipy), C2Py2, and 1,3,5-tris(4-pyridyl)2,4,6-triazine (4-TPT) grant access to multinuclear vanadocenium(III) derivatives ([(CP*V-2)(2)(mu(2)-4-BiPy)]-[BPh4](2) (21), [(CP*V-2)(2)(mu(2)-Py2C2)][BPh4](2) (24), [(Cp*V-2)(3)(mu(3)-4-TPT)][BPh4](3) (26)). Compositions of all these complexes were confirmed by single-crystal X-ray diffraction.