1-(dimethylchlorosilyl)-1-(trimethylsilyl)-2,3,4,5-tetramethylcyclopentadiene | 460740-54-9

• 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-(dimethylchlorosilyl)-1-(trimethylsilyl)-2,3,4,5-tetramethylcyclopentadiene
• 英文别名: C5Me4(SiMe3)(SiMe2Cl)；Chloro-dimethyl-(2,3,4,5-tetramethyl-1-trimethylsilylcyclopenta-2,4-dien-1-yl)silane；chloro-dimethyl-(2,3,4,5-tetramethyl-1-trimethylsilylcyclopenta-2,4-dien-1-yl)silane
• CAS: 460740-54-9
• 化学式: C₁₄H₂₇ClSi₂
• 分子量: 286.992
• InChiKey: AVVLGNYZSMAIFD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.73
• 重原子数：
  17
• 可旋转键数：
  2
• 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：

  1-(dimethylchlorosilyl)-1-(trimethylsilyl)-2,3,4,5-tetramethylcyclopentadiene 、 四氯化钛 以 二氯甲烷 为溶剂， 以83%的产率得到(1-(chlorodimethylsilyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride
  参考文献：
  名称：

  交联的（氨基甲基）聚苯乙烯上受支持的受限几何催化剂：乙烯和1-辛烯聚合的研究

  摘要：

  TiCl 4与（氯二甲基甲硅烷基）（三甲基甲硅烷基）环戊二烯的反应导致Me 3 SiCl的化学选择性消除，并干净地得到三氯化钛（（氯二甲基甲硅烷基）环戊二烯基）钛（2）。同样地，的TiCl的反应4与（chlorodimethylsilyl）（三甲基甲硅烷）四甲基环戊二烯（6）还导致在化学选择性消除的Me 3的SiCl和干净，得到（（chlorodimethylsilyl）四甲基环戊二烯）三氯化钛（7）。该观察结果与6与ZrCl 4的反应形成鲜明对比，后者导致Me的化学选择性消除。3 SiCl，但提供了半三明治和锆茂复合物的混合物。在（氨基甲基）聚苯乙烯上的配合物2或7的载体（AMPS，1％交联，1.3 wt％N，0.928 mmol N / g载体），其中选择载体中胺含量与前体催化剂的摩尔比如果将其设为3：1，则会分别导致几何约束催化剂（CGC）8或9的组装。根据29 Si NMR，在络合

  DOI：

  10.1021/om020482i

文献信息

• Titanium and zirconium chloro, oxo and alkyl derivatives containing silyl-cyclopentadienyl ligands. Synthesis and characterisation
  作者：Olga Buitrago、Gerardo Jiménez、Tomás Cuenca

  DOI：10.1016/s0022-328x(03)00430-3

  日期：2003.10

  The reaction of the tetramethylcyclopentadiene-silyl substituted derivative C5Me4(SiMe3)(SiMe2Cl) with MCl4 afforded the trichloro mono-tetramethylcyclopentadienyl complexes M(eta(5)-C5Me4SiMe2Cl)Cl-3 [M = Ti (1), Zr (2)] with selective elimination of SiMe3Cl. Compound 1 reacts with deoxygenated water in methylene chloride, with the evolution of HCl, to give the dinuclear titanium compound Ti[mu-(eta(5)-C5Me4SiMe2O-kappaO)]Cl-2}(2) (3), which was converted into the mu-oxo complex Ti[mu-(eta(5)-C5MC4SiMe2O-kappaO)]Cl}(2)(mu-O) (4) by a further hydrolysis reaction which occurred when a solution of 3 in toluene was refluxed for a long period of time in the air. Depending on the size of the alkyl ligand, reactions of the mononuclear compound 1 with an appropriate alkylating reagent rendered the peralkylated Ti(eta(5)-C5Me4SiMe2R)R-3 [R = Me (5), CH2Ph (6)] or partially alkylated Ti[(eta(5)-C5Me4SiMe2(CH2SiMe3)]Cl(CH2SiMe3)(2)} (7) compounds by a salt metathesis route. Attempts to synthesise a partially methylated or benzylated complex were unsuccessful. Treatment of the dinuclear compound 3 with four equivalents of MgClMe yielded the tetramethyl derivative Ti[mu-(eta(5)-C5Me4SiMe2O-KO)]Me-2}(2) (8), while the same reaction carried out with MgCl(CH2Ph) or Mg(CH2Ph)(2).2THF gave the chloro-benzyl derivative Ti[mu-(eta(5)-C5Me4SiMe2O-kappaO)]Cl(CH2Ph)}(2) (9) as an equimolar mixture of diastereomers, regardless of the molar ratio of the alkylating reagent used. All of the new compounds were characterised by elemental analysis and NMR spectroscopy. (C) 2003 Elsevier B.V. All rights reserved.