1,2,4-Tris-(trimethylsilyl)cyclopentadien | 41991-86-0

• 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: 1,2,4-Tris-(trimethylsilyl)cyclopentadien
• 英文别名: 1,2,4-tris(trimethylsilyl)cyclopentadiene；[2,4-Bis(trimethylsilyl)cyclopenta-2,4-dien-1-yl]-trimethylsilane
• CAS: 41991-86-0
• 化学式: C₁₄H₃₀Si₃
• 分子量: 282.649
• InChiKey: BEQTXYOHRBLJDZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.32
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  三氯一茂钛 、 1,2,4-Tris-(trimethylsilyl)cyclopentadien 在 LiC₄H₉ 作用下， 以 正己烷 、 苯 为溶剂， 以61%的产率得到dichloro(η5-cyclopentadienyl)(η5-tris-1,2,4-trimethylsilylcyclopentadienyl)titanium(IV)
  参考文献：
  名称：

  Approaches to hexane-soluble cationic organometallic Lewis acids. Synthesis, structure, and reactivity of titanocene derivatives containing polysilylated cyclopentadienyl ligands

  摘要：

  A series of titanocene dichloride derivatives was synthesized where the total trimethylsilyl substitution on the two cyclopentadienyl rings was 0, 2, 3, 4, and 5. Treatment of these complexes with methyllithium afforded 88-93% yields of the dimethyl derivatives, while reaction of the dichlorides with silver tetrafluoroborate afforded 45-57% yields of the difluoro derivatives. However, 1,1',2,3',4-pentakis(trimethylsilyl)titanocene dichloride afforded complex reaction mixtures upon treatment with either methyllithium or silver tetrafluoroborate. Complexes containing three and four trimethylsilyl groups afforded moderately stable cationic intermediates. The cationic complex derived from 1,1',3,3'-tetrakis(trimethylsilyl)titanocene dichlonue and silver tetrafluoroborate was the most stable and was partially characterized by H-1, F-19, and C-13 NMR and IR spectroscopy. The barrier to cyclopentadienyl rotation was examined for 1,1',3,3'-tetrakis(trimethylsilyl)titanocene dichloride and 1,1',3,3'-tetrakis(trimethylsilyl)titanocene difluoride and was found to be 8.9 +/- 0.5 kcal/mol for both complexes. The X-ray crystal structures of 1,1',3,3'-tetrakis(trimethylsilyl) titanocene difluoride and 1,1',2,4-tetrakis(trimethylsilyl)titanocene difluoride were determined to probe for steric distortions. 1,1',3,3'-Tetrakis(trimethylsilyl)titanocene difluoride crystallizes in the orthorhombic space group Pbna with a = 8.788 (9) angstrom, b = 18.093 (2) angstrom, c = 18.585 (2) angstrom, V = 2954.8 (9) angstrom3, and Z = 4. 1,1',2,4-Tetrakis(trimethylsilyl)titanocene difluoride crystallizes in the triclinic space group P1BAR with a = 9.2476 (5) angstrom, b = 10.6838 (15) angstrom, c = 15.8842 (19) angstrom, alpha = 106.754 (10)-degrees, beta = 96.727 (8)-degrees, gamma = 99.291 (8)-degrees, V = 1456.9 (3) angstrom3, and Z = 2.

  DOI：

  10.1021/ic00036a017
• 作为产物：
  描述：

  (η⁵ -1,2,4-(Me₃Si)₃C₅H₂)₂Th(bipy) 在 水 作用下， 以 氘代苯 为溶剂， 生成 2,2'-联吡啶 、 1,2,4-Tris-(trimethylsilyl)cyclopentadien
  参考文献：
  名称：

  [η5-1,2,4-(Me3Si)3C5H2]2Th(bipy)的合成、结构及其小分子反应活性

  摘要：

  (Cp 3tms ) 2 ThCl 2 ( 1 ; Cp 3tms = η 5 -1,2,4-(Me 3 Si) 3 C 5 H 2 ) 与 Me 3 SiI 的卤化物交换提供 (Cp 3tms ) 2 ThI 2 ( 2 )，然后在 2,2'-联吡啶存在下用钾石墨 (KC 8 ) 还原，以良好的收率得到钍联吡啶茂金属 (Cp 3tms ) 2 Th(bipy) ( 3 )。配合物3已得到充分表征，并且易于与各种小分子反应。例如，当暴露于CuI、Ph 2 S 2 、有机叠氮化物和CS 2时， 3可以充当(Cp 3tms ) 2 Th(II)片段的合成等价物。 此外，添加硫代二苯甲酮Ph 2 CS、对甲基苯甲醛( p -MeC 6 H 4 )CHO、二苯甲酮Ph 2 CO、酰胺化物PhCONH(对甲苯基)、硒代酮( p , p'-二甲氧基)、硒代二苯甲酮( p -MeOPh) 2 CSe、二(对甲苯基)甲胺(

  DOI：

  10.1021/acs.inorgchem.4c00635

文献信息

• Synthesis and structure of mono-THF solvates of bis(cyclopentadienyl)samarium(II) complexes: (C5Me5)2 Sm(THF) and [C5H2(SiMe 3)3][C5H3(SiMe3)2]Sm(THF)
  作者：William J. Evans、Gabriele Kociok-Köhn、Samuel E. Foster、Joseph W. Ziller、Robert J. Doedens

  DOI：10.1016/0022-328x(93)83055-z

  日期：1993.2

  organosamarium(II) complexes (C5Me5)2Sm(THF) and [C5H2(SiMe3)3][C5H3)(SiMe3)2]Sm(THF). (C5Me5)2]Sm(THF). (C5Me5)2Sm(THF) crystallizes from toluene in space group P21/n with a = 9.7606(13), b = 16.6557(17), c = 14.0710(16) Å, β = 90.446(10)°, V = 2287.4(5) Å3 and Dcalcd = 1.431 g cm−3 for Z = 4. Least-squares refinement of the model based on 2879 reflections converged to a final RF = 3.1%. [C5H2(SiMe3)3][C5H3(

  已获得有机sa（II）配合物（C 5 Me 5）2 Sm（THF）和[C 5 H 2（SiMe 3）3 ] [C 5 H 3）的单THF溶剂化物的X射线晶体学数据。（SiMe 3）2 ] Sm（THF）。（C 5 Me 5）2 ] Sm（THF）。（C 5 Me 5）2 Sm（THF）从空间群P 2 1 / n中的甲苯结晶，其a = 9.7606（13），b= 16.6557（17），C ^ = 14.0710（16）A，β= 90.446（10）°，V = 2287.4（5）3和d计算值=1.431克厘米-3为Ž = 4最小二乘法修正的基于2879个反射的模型最终收敛到R F = 3.1％。[C 5 H ^ 2（森达3）3 ] [C 5 H ^ 3（森达3）2] -Sm（THF）}（C 6 H ^ 12）0.5从己烷中结晶，空间群P与一个= 9.3600（17） ，b = 11.0311（21），C
• Approaches to hexane-soluble cationic organometallic Lewis acids. Synthesis, structure, and reactivity of titanocene derivatives containing polysilylated cyclopentadienyl ligands
  作者：Charles H. Winter、Xiao Xing Zhou、Mary Jane Heeg

  DOI：10.1021/ic00036a017

  日期：1992.5

  A series of titanocene dichloride derivatives was synthesized where the total trimethylsilyl substitution on the two cyclopentadienyl rings was 0, 2, 3, 4, and 5. Treatment of these complexes with methyllithium afforded 88-93% yields of the dimethyl derivatives, while reaction of the dichlorides with silver tetrafluoroborate afforded 45-57% yields of the difluoro derivatives. However, 1,1',2,3',4-pentakis(trimethylsilyl)titanocene dichloride afforded complex reaction mixtures upon treatment with either methyllithium or silver tetrafluoroborate. Complexes containing three and four trimethylsilyl groups afforded moderately stable cationic intermediates. The cationic complex derived from 1,1',3,3'-tetrakis(trimethylsilyl)titanocene dichlonue and silver tetrafluoroborate was the most stable and was partially characterized by H-1, F-19, and C-13 NMR and IR spectroscopy. The barrier to cyclopentadienyl rotation was examined for 1,1',3,3'-tetrakis(trimethylsilyl)titanocene dichloride and 1,1',3,3'-tetrakis(trimethylsilyl)titanocene difluoride and was found to be 8.9 +/- 0.5 kcal/mol for both complexes. The X-ray crystal structures of 1,1',3,3'-tetrakis(trimethylsilyl) titanocene difluoride and 1,1',2,4-tetrakis(trimethylsilyl)titanocene difluoride were determined to probe for steric distortions. 1,1',3,3'-Tetrakis(trimethylsilyl)titanocene difluoride crystallizes in the orthorhombic space group Pbna with a = 8.788 (9) angstrom, b = 18.093 (2) angstrom, c = 18.585 (2) angstrom, V = 2954.8 (9) angstrom3, and Z = 4. 1,1',2,4-Tetrakis(trimethylsilyl)titanocene difluoride crystallizes in the triclinic space group P1BAR with a = 9.2476 (5) angstrom, b = 10.6838 (15) angstrom, c = 15.8842 (19) angstrom, alpha = 106.754 (10)-degrees, beta = 96.727 (8)-degrees, gamma = 99.291 (8)-degrees, V = 1456.9 (3) angstrom3, and Z = 2.
• Synthesis and Structure of [η⁵-1,2,4-(Me₃Si)₃C₅H₂]₂Th(bipy) and Its Reactivity toward Small Molecules
  作者：Shichun Wang、Dongwei Wang、Yi Heng、Tongyu Li、Wanjian Ding、Guofu Zi、Marc D. Walter

  DOI：10.1021/acs.inorgchem.4c00635

  日期：2024.4.22

  Halide exchange of (Cp3tms)2ThCl2 (1; Cp3tms = η5-1,2,4-(Me3Si)3C5H2) with Me3SiI furnishes (Cp3tms)2ThI2 (2), which is then reduced with potassium graphite (KC8) in the presence of 2,2′-bipyridine to give the thorium bipyridyl metallocene (Cp3tms)2Th(bipy) (3) in good yield. Complex 3 was fully characterized and readily reacted with various small molecules. For example, 3 may serve as a synthetic

  (Cp 3tms ) 2 ThCl 2 ( 1 ; Cp 3tms = η 5 -1,2,4-(Me 3 Si) 3 C 5 H 2 ) 与 Me 3 SiI 的卤化物交换提供 (Cp 3tms ) 2 ThI 2 ( 2 )，然后在 2,2'-联吡啶存在下用钾石墨 (KC 8 ) 还原，以良好的收率得到钍联吡啶茂金属 (Cp 3tms ) 2 Th(bipy) ( 3 )。配合物3已得到充分表征，并且易于与各种小分子反应。例如，当暴露于CuI、Ph 2 S 2 、有机叠氮化物和CS 2时， 3可以充当(Cp 3tms ) 2 Th(II)片段的合成等价物。 此外，添加硫代二苯甲酮Ph 2 CS、对甲基苯甲醛( p -MeC 6 H 4 )CHO、二苯甲酮Ph 2 CO、酰胺化物PhCONH(对甲苯基)、硒代酮( p , p'-二甲氧基)、硒代二苯甲酮( p -MeOPh) 2 CSe、二(对甲苯基)甲胺(