(N(Me3SiNCH2CH2)3)ZrPHC2H4PH2 | 1093406-74-6

• 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
• 英文名称: (N(Me3SiNCH2CH2)3)ZrPHC2H4PH2
• CAS: 1093406-74-6
• 化学式: C₁₇H₄₆N₄P₂Si₃Zr
• 分子量: 544.007
• InChiKey: DATXKTUCWPAUAK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  ([κ5-N,N,N,N,C-(Me3SiNCH2CH2)2NCH2CH2NSiMe2CH2]Zr 、 1,2-双(膦酰)乙烷 以 乙醚 为溶剂， 以76%的产率得到(N(Me3SiNCH2CH2)3)ZrPHC2H4PH2
  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

文献信息

• Triamidoamine-supported zirconium complexes in the catalytic dehydrocoupling of 1,2-bisphosphinobenzene and -ethane
  作者：Michael B. Ghebreab、Tamila Shalumova、Joseph M. Tanski、Rory Waterman

  DOI：10.1016/j.poly.2009.05.074

  日期：2010.1

  The readily prepared zirconium complex, [K-5-(Me3SiNCH2CH2)(2)NCH2CH2NSiMe2CH2]Zr (1), is an effective precatalyst in the dehydrocoupling of o-bisphosphinobenzene and 1,2-bisphosphinoethane to the known intercalated products. The phosphanido complex (N3N)Zr[K-2-1,2-PH(PH2)C6H4] (N3N=N(CH2CH2NSiMe3)(3)(3-)), 2 was prepared independently by reaction of 1 with o-bisphosphinobenzene. Complex 2 was identified as an intermediate zirconium complex in the catalytic dehydrocoupling of o-bisphosphinobenzene. Likewise, previously reported (N3N)Zr(PHCH2CH2PH2) (3) was identified in the catalytic dehydrocoupling of 1,2-bisphosphinoethane. Investigation of the thermal decomposition of 2 and the reactivity of 2 with stoichiometric o-bisphosphinobenzene suggest that the catalysis proceeds via sequential P-P bond forming steps. The solid state structure of 2, which features a six-coordinate (N3N)Zr-complex, is reported. (C) 2009 Elsevier Ltd. All rights reserved.