| 1093406-79-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• CAS: 1093406-79-1
• 化学式: C₁₉H₄₉N₅Si₃Zr
• 分子量: 523.112
• InChiKey: ZWGRACUBSLOLGE-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  、 N,N'-二异丙基碳二亚胺 以 neat (no solvent) 为溶剂， 以65%的产率得到2-[bis(2-trimethylsilylazanidylethyl)amino]ethyl-[N,N'-di(propan-2-yl)-N-trimethylsilylcarbamimidoyl]azanide;tert-butylazanide;zirconium(4+)
  参考文献：
  名称：

  C–N Bond formation via ligand-induced nucleophilicity at a coordinated triamidoamine ligand

  摘要：

  (N3N)ZrX 复合物（X = 氨基、Clâ、CH3â）与碳化二亚胺底物反应时，会插入三氨基胺配体的 ZrâN 键，而不是 ZrâX 键，这一点在相关的 (N3N)ZrX 复合物（X = PR2â、AsR2â）中也有观察到。

  DOI：

  10.1039/c1cc15179g
• 作为产物：
  描述：

  叔丁胺 、 ([κ5-N,N,N,N,C-(Me3SiNCH2CH2)2NCH2CH2NSiMe2CH2]Zr 以 苯 为溶剂， 以73%的产率得到
  参考文献：
  名称：

  General Preparation of (N₃N)ZrX (N₃N = N(CH₂CH₂NSiMe₃)₃³⁻) Complexes from a Hydride Surrogate

  摘要：

  A homoleptic triamidoamine zirconium complex featuring a metalated trimethylsilyl substituent, [k(5)- (Me3SiNCH2CH2)(2)NCH2CH2NSiMe2CH2]Zr (1), was synthesized by reaction of Zr(CH2Ph)(4) with N(CH(2)CH(2)NHSiN(4)e(3))(3) followed by sublimation. Complex 1 is a general precursor to a family of complexes with the formulation (N3N)ZrX (N3N = N(CH2CH2NSiMe3)(3)(3-), X = anionic ligand) by reactions that parallel expected reactivity of a hydride derivative. Treatment of 1 with phosphines, amines, thiols, alkynes, and phenol resulted in the formation of new, pseudo-C-3v-symmetric (N3N)ZrX complexes (X = phosphido, amido, alkynyl, thiolate, or phenoxide) via element-H bond activation. Thus, the reactivity of complex I is that best described as a hydride surrogate. For example, complex I reacted with PhPH2 at ambient temperature to provide (N3N)ZrPHPh (2) in 86% yield. Density functional theory studies and X-ray crystal structures provide a general overview of the bonding in these complexes, which appears to be highly ionic. In general, there is little evidence for ligand-to-metal pi-bonding for the pseudoaxial X ligand in these complexes except for strongly pi-basic terminal amido ligands. The limited pi-bonding appears to be the result of competitive pi-donation by the pseudoequatorial amido arms of the triamidoamine ancillary ligand. Thus, the relative Zr-X bond energies are governed by the basicity of the anionic ligand X. Solid-state structures of phosphido (3, 4, 5), amido (10), and thiolate (15) complexes support the computational results.

  DOI：

  10.1021/om8008684