amidobis(pentamethylpentacyclopentadienyl)titanium(III) | 165965-93-5

• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: amidobis(pentamethylpentacyclopentadienyl)titanium(III)
• 英文别名: azanide;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;titanium(3+)
• CAS: 165965-93-5
• 化学式: C₂₀H₃₂NTi
• 分子量: 334.361
• InChiKey: RSLKZCZOUWELTP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.61
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  1
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (CH3)bis(η(5)-pentamethylpentacyclopentadienyl)titanium(III) 、 氨 以 正己烷 为溶剂， 以58%的产率得到amidobis(pentamethylpentacyclopentadienyl)titanium(III)
  参考文献：
  名称：

  A π-Donor Spectrochemical Series for X in (Me₅C₅)₂TiX, and β-Agostic Interactions in X = Et and N(Me)Ph

  摘要：

  The EPR and electronic spectra of d(1)-bent metallocene compounds of the type Cp*(2)TiX, where X is halide, alkoxide, amide, alkyl, or hydride and Cp* = Me(5)C(5), have been studied. Several of these compounds are new, and those with X = N(Me)H and F were characterized by X-ray crystallography. The crystal structure of Cp*2TiN(Me)H showed that the N(Me)H ligand lies on the plane defined by Cp*(centroid)-Ti-Cp*(centroid). This is the sterically most unfavorable conformation but allows maximum Ti-N pi-bonding. The anisotropic frozen solution EPR spectra were analyzed by the method used by Petersen and Dahl for the d(1)-metallocenes, Cp(2)VX(2), which gives g(x), g(y), and g(z). Although the values of g(x) and g(z) are relatively constant throughout the series, the value of g(y) varies with the pi-donor ability of X. The pi-donor series is N(Me)H approximate to NH2 approximate to OMe > OPh approximate to F > N(Me)Ph Cl > Br > I > H. Among the known alkyls, the pi-donor ability was Et > Me > n-Pr approximate to CH(2)CMe(3) > CH2C6H5, which is rationalized, in part, by a beta-agostic interaction in the case of Et. The beta-agostic interaction in Cp*(2)TiEt and in Cp*2TiN(Me)Ph was investigated by variable-temperature EPR spectroscopy giving an enthalpy and entropy for the agostic interaction. For Cp*(2)TiEt the parameters for the agostic interaction are Delta H degrees = -1.93(3) kcal/mol and Delta S degrees = -6.3(2) eu, and for Cp*2TiN(Me)Ph, Delta H degrees = -1.5(1) kcal/mol and Delta S degrees = -7.9(5) eu.

  DOI：

  10.1021/ja953272o

文献信息

• Amidobis(pentamethylcyclopentadienyl)titanium(III)
  作者：E. Brady、J. R. Telford、G. Mitchell、W. Lukens

  DOI：10.1107/s0108270194005792

  日期：1995.4.15

  The title compound, [Ti(NH2)(Me(5)C(5))(2)] (I), is a bent metallocene with the NH2 group oriented so as to maximize the pi interaction between the N and Ti atoms. The Ti-N bond length is short [1.944 (2) Angstrom], consistent with increased pi bonding.