Yb{C(SiHMe₂)₃}₂THF₂ | 1192824-31-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: Yb{C(SiHMe₂)₃}₂THF₂
• 英文别名: Yb{tris(dimethylsilyl)methyl}₂(tetrahydrofuran)₂；(tetrahydrofuran)2Yb(tris(dimethylsilyl)methyl)2；bis(dimethylsilyl)methyl-dimethylsilane;oxolane;ytterbium(2+)
• CAS: 1192824-31-9
• 化学式: C₂₂H₅₈O₂Si₆Yb
• 分子量: 696.254
• InChiKey: HDWIVSBJWIZTOV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.87
• 重原子数：
  31
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Yb{C(SiHMe₂)₃}₂THF₂ 在 air 作用下， 以 氘代苯 为溶剂， 反应 0.01h， 生成 tris(dimethylsilyl)methane
  参考文献：
  名称：

  Intermolecular β-Hydrogen Abstraction in Ytterbium, Calcium, and Potassium Tris(dimethylsilyl)methyl Compounds

  摘要：

  A series of organometallic compounds containing the tris(dimethylsilyl)methyl ligand are described. The potassium carbanions KC(SiHMe2)(3) and {KC(SiHMe2)(3)-TMEDA}(2) are synthesized by deprotonation of the hydrocarbon HC(SiHMe2)(3) with potassium benzyl. {KC(SiHMe2)(3)-TMEDA}(2) crystallizes as a dimer with two types of three-center-two-electron K-H-Si interactions: side-on coordination of SiH (angle K-H-Si = 102(2)degrees) and more obtuse K-H-Si structures (angle K-H-Si approximate to 150 degrees). The divalent calcium and ytterbium compounds M{C(SiHMe2)(3)}(2)L (M = Ca, Yb; L = 2THF, TMEDA) are prepared from MI2 and 2 equiv of KC(SiHMe2)(3). Low (1)J(SiH) coupling constants in the NMR spectra, low-energy nu(SiH) bands in the IR spectra, and short M-Si distances and small M-C-Si angles in the crystal structures suggest beta-agostic interactions on each C(SiHMe2)(3) ligand. The IR assignments of M{C(SiHMe2)(3)}(2)L (L = 2THF, TMEDA) are supported by DFT calculations. The compounds M{C(SiHMe2)(3)}(2)L react with 1 or 2 equiv of B(C6F5)(3) to give the 1,3-disilacyclobutane {Me2SiC(SiHMe2)(2)}(2) and MC(SiHMe2)(3)HB(C6F5)(3)L or M{HB(C6F5)(3)}(2)L, respectively. In addition, M{C(SiHMe2)(3)}(2)L compounds react with BPh3 to give beta-H abstracted products. The compounds M{C(SiHMe2)(3)}(2)THF2 react with SiMe3I to yield Me3SiH and disilacyclobutane as the products of beta-H abstraction, while M{C(SiHMe2)(3)}(2)TMEDA and Me3SiI form a mixture of Me3SiH and the alkylation product Me3SiC(SiHMe2)(3) in a 1:3 ratio.

  DOI：

  10.1021/om3010299

文献信息

• Lewis Acid-Mediated β-Hydride Abstraction Reactions of Divalent M(C(SiHMe₂)₃)₂THF₂ (M = Ca, Yb)
  作者：KaKing Yan、Brianna M. Upton、Arkady Ellern、Aaron D. Sadow

  DOI：10.1021/ja9070865

  日期：2009.10.28

  calcium and ytterbium compounds M(C(SiHMe(2))(3))(2)THF(2) contain beta-agostic SiH groups, as determined by spectroscopy and crystallography. Upon thermolysis, HC(SiHMe(2))(3) is formed. However, the SiH groups are hydridic. The compounds M(C(SiHMe(2))(3))(2)THF(2) react with 1 and 2 equiv of the Lewis acid B(C(6)F(5))(3) to form MC(SiHMe(2))(3)HB(C(6)F(5))(3))THF(2) and M(HB(C(6)F(5))(3))(2)THF(2), respectively

  二价钙和镱化合物 M(C(SiHMe(2))(3))(2)THF(2) 包含β-agostic SiH 组，由光谱学和晶体学确定。热解时，会形成 HC(SiHMe(2))(3)。然而，SiH 基团是氢化的。化合物 M(C(SiHMe(2))(3))(2)THF(2) 与 1 和 2 当量的路易斯酸 B(C(6)F(5))(3) 反应形成 MC( SiHMe(2))(3)HB(C(6)F(5))(3))THF(2) 和 M(HB(C(6)F(5))(3))(2)THF( 2) 分别。这些物质包含来自氢化物提取的阴离子 [HB(C(6)F(5))(3)](-) 而不是 [(Me(2)HSi)(3)CB(C(6)F(5) )(3)](-) 来自烷基提取。1,3-二硅杂环丁烷副产品最初建议β-消除[作为silene Me(2)Si 水平线C(SiHMe(2))(2) 的二聚体]，但其他产品和反应化