[(η5:σ-(C9H6)C2B10H10)Y(CH2C6H4-o-NMe2)(THF)2] | 1071146-41-2

• 英文名称: [(η5:σ-(C9H6)C2B10H10)Y(CH2C6H4-o-NMe2)(THF)2]
• CAS: 1071146-41-2
• 化学式: C₂₈H₄₄B₁₀NO₂Y
• 分子量: 623.679
• InChiKey: BZLASAUGBMMLSD-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：

  乙二醇二甲醚 、 [(η5:σ-(C9H6)C2B10H10)Y(CH2C6H4-o-NMe2)(THF)2] 以 乙二醇二甲醚 为溶剂， 以76%的产率得到[(η5:σ-(C9H6)C2B10H10)Y(CH2C6H4-o-NMe2)(DME)]*0.5THF
  参考文献：
  名称：

  Synthesis and Structural Characterization of Constrained-Geometry Organolanthanide Chlorides and Alkyls Incorporating the Ligand [η⁵:σ-(C₉H₆)C₂B₁₀H₁₀]²⁻

  摘要：

  Interaction of 1-indenyl-1,2-carborane (1) with 2 equiv of KH in refluxing THF gave the dipotassium salt [K-2][(C9H6)C2B10H10]. Treatment of [K-2][(C9H6)C2B10H10] with 1 equiv of LnCl(3) in THF generated the ionic complex [K(THF)(6)][{eta(5):sigma-(C9H6)C2B10H10}(2)La(THF)] (2) for early lanthanide or organolanthanide chloride complexes [{eta(5):sigma-(C9H6)C2B10H10}Ln(THF)(2)(mu-Cl)(2)K(THF)(2)](2) (Ln = Y (3a), Gd (3b), Er (3c), Yb (3d)) for late lanthanides. Reaction of 3 with nucleophile NaCp or KCH2C6H4-o-NMe2 afforded the corresponding salt metathesis products [eta 5:sigma-(C9H6)C2B10H10]Ln(eta(5)-C5H5)(THF)(2) (Ln = Y (4a), Gd (4b)) or [eta(5):sigma-(C9H6)C2B10H10]Ln(CH2C6H4-o-NMe2)(DME) (Ln = Y (5a), Er (5c)), respectively. Complexes 5 were also synthesized via the alkane elimination reaction of 1-indenyl-1,2-carborane with Ln(CH2C6H4-o-NMe2)(3). They represent the first examples of organolanthanide alkyl complexes incorporating a carboranyl ligand. These complexes were fully characterized by various spectroscopic techniques and elemental analyses. Some were further confirmed by single-crystal X-ray analyses.

  DOI：

  10.1021/om8006344
• 作为产物：
  描述：

  Y(CH₂C₆H₄NMe₂-o)₃ 、 1-indenyl-1,2-carborane 以 四氢呋喃 为溶剂， 以87%的产率得到[(η5:σ-(C9H6)C2B10H10)Y(CH2C6H4-o-NMe2)(THF)2]
  参考文献：
  名称：

  Synthesis and Structural Characterization of Constrained-Geometry Organolanthanide Chlorides and Alkyls Incorporating the Ligand [η⁵:σ-(C₉H₆)C₂B₁₀H₁₀]²⁻

  摘要：

  Interaction of 1-indenyl-1,2-carborane (1) with 2 equiv of KH in refluxing THF gave the dipotassium salt [K-2][(C9H6)C2B10H10]. Treatment of [K-2][(C9H6)C2B10H10] with 1 equiv of LnCl(3) in THF generated the ionic complex [K(THF)(6)][{eta(5):sigma-(C9H6)C2B10H10}(2)La(THF)] (2) for early lanthanide or organolanthanide chloride complexes [{eta(5):sigma-(C9H6)C2B10H10}Ln(THF)(2)(mu-Cl)(2)K(THF)(2)](2) (Ln = Y (3a), Gd (3b), Er (3c), Yb (3d)) for late lanthanides. Reaction of 3 with nucleophile NaCp or KCH2C6H4-o-NMe2 afforded the corresponding salt metathesis products [eta 5:sigma-(C9H6)C2B10H10]Ln(eta(5)-C5H5)(THF)(2) (Ln = Y (4a), Gd (4b)) or [eta(5):sigma-(C9H6)C2B10H10]Ln(CH2C6H4-o-NMe2)(DME) (Ln = Y (5a), Er (5c)), respectively. Complexes 5 were also synthesized via the alkane elimination reaction of 1-indenyl-1,2-carborane with Ln(CH2C6H4-o-NMe2)(3). They represent the first examples of organolanthanide alkyl complexes incorporating a carboranyl ligand. These complexes were fully characterized by various spectroscopic techniques and elemental analyses. Some were further confirmed by single-crystal X-ray analyses.

  DOI：

  10.1021/om8006344

文献信息

• Reactivity of Traditional Metal–Carbon (Alkyl) versus Nontraditional Metal–Carbon (Cage) Bonds in Organo-Rare-Earth Metal Complexes [η⁵:σ-(C₉H₆)(C₂B₁₀H₁₀)]Ln(CH₂C₆H₄-<i>o</i>-NMe₂)(THF)₂
  作者：Jingying Yang、Zuowei Xie

  DOI：10.1021/om501212e

  日期：2015.6.8

  Equimolar reaction of 1-indenyl-1,2-carborane with Ln(CH2C6H4-o-NMe2)(3) in THF gave highly constrained-geometry complexes [eta(5):sigma-(C9H6)C2B10H10]Ln(CH2C6H4-o-NMe2)(THF)(2) (Ln = Y (1a), Gd (1b), Dy (1c)). They reacted with RN=C=NR or 2,6-Me2C6H3NCS to generate the Ln-C-alkyl insertion products [eta(5):sigma-(C9H6)C2B10H10]Ln-(eta(2)(RN)(2)C(CH2C6H4-o-NMe2)](THF) (R = TMS, Ln = Y (2a), Gd (2b); R = Bu-t, Ln = Y (2a), Gd (2b); R = Bu-t, Ln = Y (3a)) or [eta(5):sigma-(C9H6)C2B10H10]Dy[eta(2)-(2,6-Me2C6H3)NC(CH2C6H4-o-NMe2)S](THF)(2) (4c). Treatment of 2a with I equiv of R'N=C=NR' to give the Y-C-cage insertion complexes [eta(5):sigma-(C9H6)N(R')C(=NR')}C2B10H10]Y[eta(2)-(TMS)N}(2)C(CH2C6H4-o-NMe2)] (R' = Cy (5a), Pr-i (6a)). Similarly, unsaturated compounds Ph2C=C=O and PY2C=O (Py = 2-pyridyl) also inserted into the Y-C-cage bond in 2a to yield [eta(5):sigma-(C9H6)OC(=CPh2)}C2B10H10]Y[eta(2)-(TMS)N}(2)C(CH2C6H4-o-NMe2)] (7a) and [eta(5):sigma-(C9H6)OC(Py)(2)}C2B10H10]Y[eta(2)-(TMS)N)}(2)C(CH2C6H4-o-NMe2)](THF) (8a), respectively. In sharp contrast to the earlier reports that the nontraditional metal-C-cage sigma bonds in metal carboranyl complexes are generally inert toward electrophiles, the insertion of unsaturated molecules into the Y-C-cage sigma bond in 2a represents the first example of this type of reactions. These results shed some light on how to activate the nontraditional metal-carbon (cage) bonds in metal-Carboranyl complexes. All new complexes were characterized by spectroscopic techniques and elemental analyses. Some were further confirmed by single-crystal X-ray analyses.