[tert-butyl(dimethylindenylsilyl)amido]dimethyltitanium | 182166-91-2

• 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: [tert-butyl(dimethylindenylsilyl)amido]dimethyltitanium
• 英文别名: Ti(η(5):η(1)-C9H6SiMe2NCMe3)Me2；[(η5-C9H6)(SiMe2-N-t-Bu)TiMe2]；tert-butyl-[inden-1-id-1-yl(dimethyl)silyl]azanide;carbanide;titanium(4+)
• CAS: 182166-91-2
• 化学式: C₁₇H₂₇NSiTi
• 分子量: 321.374
• InChiKey: CKKGWERAHPRGDY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  Ti(η(5):η(1)-C9H6SiMe2NCMe3)Cl2 、 甲基氯化镁 以 四氢呋喃 、 正己烷 为溶剂， 以49%的产率得到[tert-butyl(dimethylindenylsilyl)amido]dimethyltitanium
  参考文献：
  名称：

  Linked amido-indenyl complexes of titanium

  摘要：

  Titanium complexes Ti(eta(5):eta(1)-C(9)H(6)SiMe(2)NCMe(3))X(2) (X = Cl, Me, CH(2)SiMe(3), CH(2)Ph) containing the tert-amido-functionalized indenyl ligand C(9)H(6)SiMe(2)NCMe(3) have been synthesized by the reaction of the dilithium derivative Li-2[C(9)H(6)SiMe(2)NCMe(3)] with TiCl3 (THF)(3) followed by oxidation or by the alkylation of the dichloro derivative. Unexpectedly, the reaction of C9H6(SiMe(3))(SiMe(2)Cl) with TiCl4 does not give Ti(eta(5)-C(9)H(6)SiMe(2)Cl)Cl-3.

  DOI：

  10.1016/0022-328x(96)06350-4

文献信息

• Indenyl-amido titanium and zirconium dimethyl complexes: improved synthesis and use in propylene polymerization
  作者：Luigi Resconi、Isabella Camurati、Cristiano Grandini、Marilisa Rinaldi、Nicoletta Mascellani、Orazio Traverso

  DOI：10.1016/s0022-328x(02)01853-3

  日期：2002.12

  The synthesis of a series of indenyl amido titanium dimethyl complexes, by means of the direct synthesis from the ligand, a 2-fold excess of MeLi, and TiCl4 is reported. The H-1 NMR spectra of the complexes show a quartet structure for the metal-bound methyl groups, due to through-metal proton-proton coupling. Coupling of Ti-methyl protons with protons on the Cp ring is also revealed by COSY 2D-NMR. The performance of the Ti complexes in propylene polymerization, including [Me2Si(Me4C5)(t-BuN)]TiMe2 (1-TiMe2), [Me2Si(Ind)(t-BuN)]TiMe2 (2-TiMe2) and six other methyl titanium complexes bearing substituted indenyl ligands, has been investigated with different cocatalysts and at different polymerization temperatures and propylene concentrations. All complexes produce amorphous polypropylene (am-PP). The catalytic activity and molecular weight strongly depend on the substitution of the Cp ring: 2-TiMe2 gives polymers of lower molecular weight, while the presence of a methyl group in position 2 (as in 3-TiMe2) determines up to 4-fold increase in molecular weight. The type of cocatalyst influences mainly the catalytic activity, the borates being better activators than MAO, but also molecular weight, with again the borates giving higher molecular weights than MAO. 5-TiMe2-Ph3CB(C6F5)(4) shows an overall activation energy of polymerization of 7.35 kcal mol(-1). The rate of chain release is first order in monomer. The following activation energies for overall chain release have been calculated: DeltaDeltaE(double dagger) 2-TiMe2 = 3.4 kcal mol(-1), DeltaDeltaE(double dagger) 5-TiMe2 = 3.8 kcal mol(-1), AAET 3-TiMe2 = 6.3 kcal mol(-1). Even if all the polymers produced are amorphous, 2-TiMe2 and 5-TiMe2 show a microstructure unbalanced towards isotacticity, while 3-TiMe2, 6-TiMe2 and 8-TiMe2 are syndiotactic-enriched. Chiral induction comes mainly from a weak enantiomorphic site control. (C) 2002 Elsevier Science B.V. All rights reserved.
• Polymerization of propylene with [t-BuNSiMe2Ind]TiMe2–MAO catalyst systems
  作者：Kei Nishii、Tomiki Ikeda、Munetaka Akita、Takeshi Shiono

  DOI：10.1016/j.molcata.2004.12.035

  日期：2005.4

  ansa-Indenylamidodimethyltitanium complex ([t-BuNSiMe(2)Ind]TiMe2:1) was synthesized by one-pot reactions starting from the ligand, MeLi and TiCl4. The structure of 1 was determined by X-ray crystallography and the results obtained revealed that the indenyl ligand coordinate to titanium in an eta(4)-tendency. Propylene polymerization was conducted with I in toluene or heptane as solvent at 0 degrees C in the presence of dried methylaluminoxane (MAO) or dried modified MAO (MMAO), which was prepared from the toluene solutions of MAO or MMAO by removing free trialkylaluminium contained. Polymerization behavior was investigated from the consumption rate of propylene in a semi-batch system. The dried MAO/toluene system showed the highest activity without any deactivation. The produced polymer in the dried MAO/toluene system had the highest molecular weight and narrowest molecular weight distribution. The number-average molecular weight of the polymer increased almost linearly with increasimg polymerization time accompanied by narrowing molecular weight distribution from 1.42 to 1.37 and the number of polymer chains was almost constant. Thus, it was found that quasi-living polymerization of propylene proceeded. The C-13 NMR measurement indicated that 1-dried MAO/toluene produced poly(propylene) with isotactic triad of 40%. (c) 2005 Elsevier B.V. All rights reserved.