[Ti(III)(η5-C5Me5)2(OPh)] | 174225-45-7

• 英文名称: [Ti(III)(η5-C5Me5)2(OPh)]
• CAS: 174225-45-7
• 化学式: C₂₆H₃₅OTi
• 分子量: 411.443
• InChiKey: HNWHGMWFUYWUMZ-UHFFFAOYSA-M

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

• 作为反应物：
  描述：

  cyclopentadienylmolybdenum tricarbonyl dimer 、 [Ti(III)(η5-C5Me5)2(OPh)] 以 甲苯 为溶剂， 以70%的产率得到Cp*2Ti(OPh)(μ-CO)Mo(CO)2Cp
  参考文献：
  名称：

  钛氧烷（III）诱导的金属羰基二聚体的金属键断裂，钛醇盐在异双金属配合物中的作用,钛氧烷（III）诱导的金属羰基二聚体的金属键断裂，钛醇盐在异双金属配合物中的作用

  摘要：

  一系列钛茂（III）醇盐L 2 Ti（III）OR其中L = Cp，R = Et（1b），t Bu（1a），2,6-Me 2 C 6 H 3（1c），2,6 -吨卜2 -4-ME-C 6 H ^ 2（1D），或L =的Cp *，R =我（2E），吨BU（图2a）中，Ph（2F）合成，并进行与[CPM反应（ CO）3 ] 2 [M = Mo，W]，[CpRu（CO）2 ] 2和Co 2（CO）8。Ti（III）前体1a，1c，2a，2e和2f与[CpM（CO）3 ] 2 [M = Mo，W]反应形成异双金属配合物L 2 Ti（OR）（μ-OC）（CO ）2 MCp [M = Mo，W]，其中Ti和M通过异羰基桥连接。用Co这些钛（III）络合物的反应2（CO）8导致形成的Ti-Co的1双核配合物，Cp2为非*的Ti（OtBu）（μ-OC）的Co（CO）3从图2a，2e中，或2F，或Ti–Co

  DOI：

  10.1016/j.jorganchem.2004.09.075
• 作为产物：
  描述：

  [(η5-pentamethylcyclopentadienyl)2TiCl] 、 lithium phenolate 以 四氢呋喃 为溶剂， 以83%的产率得到[Ti(III)(η5-C5Me5)2(OPh)]
  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