[(η6-C5Me4SiMe2Ph)2Ti] | 511551-36-3

• 英文名称: [(η6-C5Me4SiMe2Ph)2Ti]
• 英文别名: (η5-C5Me4SiMe2Ph)2Ti
• CAS: 511551-36-3
• 化学式: C₃₄H₄₆Si₂Ti
• 分子量: 558.79
• InChiKey: KIRAYHOBFBDRJE-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

• 作为反应物：
  描述：

  [(η6-C5Me4SiMe2Ph)2Ti] 在 PbCl₂ 作用下， 以 四氢呋喃 为溶剂， 以79%的产率得到
  参考文献：
  名称：

  Synthesis and crystal structures of thermally stable titanocenes

  摘要：

  Reduction of fully substituted titanocene dichlorides [TiCl2(eta(5)-C5Me4R)(2)] (R = SiMe2CH2CH2Ph, 3; SiMe2Ph, 4; and SiMePh2, 5) with magnesium in THF proceeds via the formation of titanocene monochlorides [TiCl(eta(5)-C5Me4R)(2)] 6-8 to afford monomeric titanocenes, [Ti(eta(5)-C5Me4R)(2)], 9-11. Titanocene monochlorides give the expected EPR spectra in toluene solution and glass. The structure of 7 was further corroborated by single-crystal X-ray diffraction. Titanocenes 9-11 are EPR silent down to -196 degreesC but exhibit paramagnetic broadening of the signals in solution NMR spectra. The positions of the NMR signals are temperature-dependent, obeying the Curie Law in the range investigated (0-60 degreesC). As revealed by X-ray crystallography, titanocenes 9 and 11 possess bent metallocene structures with the cyclopentadienyl rings tilted at an angle of 9.8(l) and 14.4(2)degrees, respectively. Titanocenes 9-11 are easily oxidized with PbCl2 to the parent dichloride complexes 3-5. Titanocenes 9 and 10 react with bis(trimethylsilyl)ethyne (btmse) only in large excess of the alkyne to give an equilibrium concentration of the respective [Ti(eta(5)-C5Me4R)(2)(eta(2)-Me3SiC drop CSiMe3)] complexes. On the other hand, titanocene 11 does not observably react with btmse. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(02)01726-6
• 作为产物：
  描述：

  在 Mg 作用下， 以 四氢呋喃 为溶剂， 以50%的产率得到[(η6-C5Me4SiMe2Ph)2Ti]
  参考文献：
  名称：

  Synthesis and crystal structures of thermally stable titanocenes

  摘要：

  Reduction of fully substituted titanocene dichlorides [TiCl2(eta(5)-C5Me4R)(2)] (R = SiMe2CH2CH2Ph, 3; SiMe2Ph, 4; and SiMePh2, 5) with magnesium in THF proceeds via the formation of titanocene monochlorides [TiCl(eta(5)-C5Me4R)(2)] 6-8 to afford monomeric titanocenes, [Ti(eta(5)-C5Me4R)(2)], 9-11. Titanocene monochlorides give the expected EPR spectra in toluene solution and glass. The structure of 7 was further corroborated by single-crystal X-ray diffraction. Titanocenes 9-11 are EPR silent down to -196 degreesC but exhibit paramagnetic broadening of the signals in solution NMR spectra. The positions of the NMR signals are temperature-dependent, obeying the Curie Law in the range investigated (0-60 degreesC). As revealed by X-ray crystallography, titanocenes 9 and 11 possess bent metallocene structures with the cyclopentadienyl rings tilted at an angle of 9.8(l) and 14.4(2)degrees, respectively. Titanocenes 9-11 are easily oxidized with PbCl2 to the parent dichloride complexes 3-5. Titanocenes 9 and 10 react with bis(trimethylsilyl)ethyne (btmse) only in large excess of the alkyne to give an equilibrium concentration of the respective [Ti(eta(5)-C5Me4R)(2)(eta(2)-Me3SiC drop CSiMe3)] complexes. On the other hand, titanocene 11 does not observably react with btmse. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(02)01726-6

文献信息

• Dinitrogen Complexes of Bis(cyclopentadienyl) Titanium Derivatives: Structural Diversity Arising from Substituent Manipulation
  作者：Tamara E. Hanna、Emil Lobkovsky、Paul J. Chirik

  DOI：10.1021/om900282u

  日期：2009.7.27

  family of bis(cyclopentadienyl)titanium sandwich complexes, (η5-C5Me4R)2Ti (R = alkyl, aryl, silyl), has been systematically evaluated by in situ solution infrared spectroscopy. The maximum temperature of N2 coordination (Tmax) has been determined as a function of cyclopentadienyl substituent and has been correlated with the structural type (monomer or dimer) of the resulting dinitrogen complex. The electronic

  二氮协调到一个家庭双（环戊二烯基）钛的夹心复合，（η的5 -C 5我4 R）2的Ti（R =烷基，芳基，甲硅烷基），进行了系统的原位溶液评价红外光谱。已经确定了N 2配位的最高温度（T max）是环戊二烯基取代基的函数，并且已与所得二氮配合物的结构类型（单体或二聚体）相关。每个钛夹心复合物的电子特性是由二羰基衍生物的红外光谱，并通过相应的二茂铁的氧化电位进行评估，（η 5 -C 5Me 4 R）2 Fe。根据这些数据，已经确定了N 2配位的热力学偏好，并且随着较小的正电取代基的增加而增加。
• Dihydrogen and Silane Addition to Base-Free, Monomeric Bis(cyclopentadienyl)titanium Oxides
  作者：Tamara E. Hanna、Emil Lobkovsky、Paul J. Chirik

  DOI：10.1021/ic070205+

  日期：2007.4.1

  Synthesis of a family of monomeric, base-free bis(cyclopentadienyl)titanium oxide complexes, (eta5-C5Me4R)2Ti=O (R = iPr, SiMe3, SiMe2Ph), has been accomplished by deoxygenation of styrene oxide by the corresponding sandwich compound. One example, (eta5-C5Me4SiMe2Ph)2Ti=O, was characterized by X-ray diffraction. All three complexes undergo clean and facile hydrogenation at 23 degrees C, yielding the

  已通过相应的夹心化合物对苯乙烯氧化物进行脱氧，完成了一系列单体，无碱的双（环戊二烯基）钛氧化物配合物（eta5-C5Me4R）2Ti = O（R = iPr，SiMe3，SiMe2Ph）的合成。一个实例，（eta5-C5Me4SiMe2Ph）2Ti ＝ O，通过X射线衍射表征。所有这三种配合物均在23°C下进行清洁且容易的氢化反应，生成钛茂烃羟基氢化物配合物（eta5-C5Me4R）2Ti（OH）H。对于（eta5-C5Me4SiMe3）2Ti = O，氢化动力学在二氢中是一级的，并且在23°C时具有2.7（3）的正态一级动力学同位素效应，与1,2-加成途径一致。对于硅烷添加，确定了相同方向但幅度较小的同位素效应。
• Mono(dinitrogen) and Carbon Monoxide Adducts of Bis(cyclopentadienyl) Titanium Sandwiches
  作者：Tamara E. Hanna、Emil Lobkovsky、Paul J. Chirik

  DOI：10.1021/ja061213c

  日期：2006.5.1

  silyl-substituted titanocene complex, (eta5-C5Me4SiMe2Ph)2Ti, coordinates dinitrogen upon cooling to -35 degrees C to yield an unprecedented example of a mono(dinitrogen) complex of a substituted bis(cyclopentadienyl) titanium compound, (eta5-C5Me4SiMe2Ph)2Ti(N2). Analogous monocarbonyl derivatives, (eta5-C5Me4R)2Ti(CO) (R = SiMe3, SiMe2Ph, CHMe2), have been prepared by mixing the dicarbonyl compounds with the

  甲硅烷基取代的二茂钛络合物 (eta5-C5Me4SiMe2Ph)2Ti 在冷却至 -35 摄氏度时与二氮配位，以产生取代双（环戊二烯基）钛化合物（eta5-C5Me4SiMe2Ph）的单（二氮）络合物的前所未有的例子2Ti(N2)。类似的单羰基衍生物，(eta5-C5Me4R)2Ti(CO)（R = SiMe3，SiMe2Ph，CHMe2），已经通过将二羰基化合物与相应的夹层混合来制备。(eta5-C5Me4SiMe2Ph)2Ti(N2) 和 (eta5-C5Me4SiMe2Ph)2Ti(CO) 均已通过 X 射线衍射表征，并且还通过原位红外光谱观察到混合的 N2-CO 二茂钛配合物。