(η5:η1-C5H4CH2CH2PPh2)TiCl3 | 670239-89-1

• 英文名称: (η5:η1-C5H4CH2CH2PPh2)TiCl3
• CAS: 670239-89-1
• 化学式: C₁₉H₁₈Cl₃PTi
• 分子量: 431.565
• InChiKey: PDOGXKBDGCJLEM-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  四氢呋喃 、 (η5:η1-C5H4CH2CH2PPh2)TiCl3 以 四氢呋喃 为溶剂， 生成 (η5:η1-P-(C5H4)CH2CH2PPH2)titanium(IV)Cl3THF
  参考文献：
  名称：

  Crystal structures and solution dynamics of monocyclopentadienyl titanium(IV) complexes bearing pendant ether and phosphanyl type functionalities

  摘要：

  Two novel half-sandwich Ti(IV) complexes, [eta(5) :eta(1)-O-C-5(CH3)(4)CH2CH2OCH3]TiCl3 (3) and (eta(5) :eta(1) -P-C5H4CH2CH2PPh2)TiCl3 (6), were prepared and structurally characterised. At elevated temperatures, complex 3 undergoes a conversion into [eta(5) : sigma-C-5(CH3)(4)CH2CH2O-]TiCl2 (4). The dynamic behaviour of complexes 3 and 6 in solutions has been studied by variable-temperature H-1, C-13 and P-31 NMR spectroscopy. Thermodynamic parameters of the intramolecular dissociation-coordination processes for 3 and 6 were elucidated by the numerical analysis of the 6 (T) dependencies. The intramolecular M(IV)<--E (M = Ti, Zr; E = O, P) coordination in half-sandwich cyclopentadienyl complexes is discussed. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0277-5387(03)00407-8
• 作为产物：
  描述：

  四氯化钛 、 [2-(diphenylphosphanyl)ethyl]tetramethyl(trimethylsilyl)cyclopentadiene 以 甲苯 为溶剂， 以55.2%的产率得到(η5:η1-C5H4CH2CH2PPh2)TiCl3
  参考文献：
  名称：

  Crystal structures and solution dynamics of monocyclopentadienyl titanium(IV) complexes bearing pendant ether and phosphanyl type functionalities

  摘要：

  Two novel half-sandwich Ti(IV) complexes, [eta(5) :eta(1)-O-C-5(CH3)(4)CH2CH2OCH3]TiCl3 (3) and (eta(5) :eta(1) -P-C5H4CH2CH2PPh2)TiCl3 (6), were prepared and structurally characterised. At elevated temperatures, complex 3 undergoes a conversion into [eta(5) : sigma-C-5(CH3)(4)CH2CH2O-]TiCl2 (4). The dynamic behaviour of complexes 3 and 6 in solutions has been studied by variable-temperature H-1, C-13 and P-31 NMR spectroscopy. Thermodynamic parameters of the intramolecular dissociation-coordination processes for 3 and 6 were elucidated by the numerical analysis of the 6 (T) dependencies. The intramolecular M(IV)<--E (M = Ti, Zr; E = O, P) coordination in half-sandwich cyclopentadienyl complexes is discussed. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0277-5387(03)00407-8

文献信息

• 2-Phosphinothioyl- and 2-phosphinoylethylcyclopentadienyl zirconium and titanium complexes. Crystal structure of [η5:η1-C5H4CH2CH2P(O)Ph2]TiCl3
  作者：D. P. Krut’ko、M. V. Borzov、E. N. Veksler、A. V. Churakov

  DOI：10.1007/s11172-005-0226-3

  日期：2005.1

  The intracomplex conversion of (2-diphenylphosphanoethyl)cyclopentadienyl zirconium and titanium complexes into the corresponding 2-phosphinothioyl and 2-phosphinoyl derivatives, viz., (η5-C5H5)[η 5-C5H4CH2CH2P(S)Ph2]ZrCl2, [η5-C5H4CH2CH2P(S)Ph2]ZrCl3, [η5:η1C5H4CH2CH2P(O)Ph2]ZrCl3·THF, and [η5:η 1-C5H4CH2CH2P(O)Ph2]TiCl3 (7), was performed. The NMR spectroscopy data revealed the following order of

  (2-二苯基膦酰基乙基)环戊二烯基锆和钛配合物的配合物内转化为相应的2-膦硫酰基和2-膦酰基衍生物，即(η5-C5H5)[η 5-C5H4CH2CH2P(S)Ph2]ZrCl2，[η2CH2PH4进行(S)Ph2]ZrCl3、[η5:η1C5H4CH2CH2P(O)Ph2]ZrCl3·THF和[η5:η1-C5H4CH2CH2P(O)Ph2]TiCl3(7)。核磁共振谱数据揭示了官能团相对于 Zr 中心的配位能力的顺序：Ph2P=O > Ph2P > Ph2P=S。发现单齿配体（Ph3P=O > Ph3P > Ph3P=S）相对于 (η5- )ZrCl3 的顺序类似。通过X射线衍射分析确定了配合物7的分子结构。发现 Ph2P=O 基团与钛原子的配位在结晶态和溶液中均保持不变。
• Preparation of Half-Sandwich Alkyl−Titanium(IV) Complexes Stabilized by a Cyclopentadienyl Ligand with a Pendant Phosphine Tether and Their Use in the Catalytic Hydroamination of Aliphatic and Aromatic Alkynes
  作者：María L. Buil、Miguel A. Esteruelas、Ana M. López、A. Concepción Mateo

  DOI：10.1021/om060370h

  日期：2006.8.1

  regioselectivities of 100% are formed from the reactions between aliphatic alkynes and aromatic amines, while anti-Markovnikov derivatives with regioselectivies of 100% are obtained from the reactions of aromatic alkynes with all the studied amines and from the reactions of the aliphatic alkynes with tert-butylamine and dodecylamine. The reaction of 1-octyne and cyclohexylacetylene with cyclohexylamine gives

  络合物Cp P TiCl 3（1 ; Cp P = C 5 H 4 CH 2 CH 2 PPh 2）与3.0、2.0和1.0当量的MeMgCl反应生成Cp P TiMe 3（2），Cp P TiMe 2 Cl（3）和Cp P TiMeCl 2（4）。在溶液中，环戊二烯基配体的P-供体取代基参与配位-离解平衡（ΔH °= 7.7±0.1 kcal·mol - 1和ΔS °= 36.9±0.4 cal·mol - 1 ·K - 1（2），ΔH °= 6.0±0.2 kcal·mol - 1和ΔS °= 22.3±0.6 cal·mol - 1 ·K - 1（3），和Δ ħ °= 6.1±0.2千卡·摩尔- 1和Δ小号°= 24.4±1卡·摩尔- 1 ·K - 1为4）。1与3.0当量的PhCH 2 MgCl的反应得到Cp P Ti（CH 2Ph）3（5），包含在-90至20°C之间的游离膦侧基。与5相反，（2