bis(trimethylsilyl)azanide;diethylalumanylium | 6917-88-0

• 英文名称: bis(trimethylsilyl)azanide;diethylalumanylium
• CAS: 6917-88-0
• 化学式: C₁₀H₂₈AlNSi₂
• 分子量: 245.492
• InChiKey: VIDOIAMNUYKVQY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.99
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  bis[N,N-bistrimethylsilylamido]bis(tetrahydrofuran)ytterbium(II) 、 三乙基铝 以 正己烷 为溶剂， 以69%的产率得到bis(tetraethylaluminato)ytterbium(II)
  参考文献：
  名称：

  Peralkylated Ytterbium(II) Aluminate Complexes YbAl₂R₈. New Insights into the Nature of Aluminate Coordination

  摘要：

  The homoleptic ytterbium(II) tetraalkylaluminate complexes {Yb[AlR4](2)}(n) have been obtained according to a silylamide elimination reaction from Yb[N(SiMe3)(2)](2)(THF)(2) and excess AlR3 (R = Me, Et, iBu). While the tetramethylaluminate derivative is a pyrophoric powder which is insoluble in aliphatic and aromatic hydrocarbons, the ethyl and isobutyl congeners are readily soluble in n-hexane. Perethylated polymeric {Yb[AlEt4](2)}(n) is constituted formally of the two molecular fragments [Yb(AlEt4)](+) and [Yb(AlEt4)(3)](-), forming an intricate three-dimensional network in the solid state. Both fragments are linked by bridging alpha -carbon atoms and secondary Yb . . .H-C agostic interactions combining mu,eta (1), mu,eta (2), and mu,eta (3) coordination modes which result in remarkably short Yb . . . Al (2.809(2) Angstrom) and a large range of Yb . . .C (2.649(5)-3.364(6) Angstrom) distances. DFT calculations on the molecular fragments [Yb(AlEt4)(3)](-) and [Yb(AlEt4)](+) reproduced the X-ray geometry remarkably well. Moreover, the theoretical investigations on model systems for the aluminate coordination support the highly fluxional nature of the aluminate coordination (DeltaE(eta2 --> eta3) = -8 kcal/mol), which is also indicated by solution NMR spectroscopy. A topological analysis of the total electron density of the mu,eta (2)-bonded aluminate ligand in the benchmark systems Y(AlR4)(3) (R = Me, Et) revealed the presence of two bond critical points between the Y-C-b and C-b-Al bonds (C-b = bridging carbon atom) and thus suggests a hypervalent character of the bridging carbon atom.

  DOI：

  10.1021/om0102091