1-<(tert-butylamino)dimethylsilyl>indene | 135610-16-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚和异茚
• 英文名称: 1-<(tert-butylamino)dimethylsilyl>indene
• 英文别名: tert-butyl(dimethylindenylsilyl)amine；Silanamine, N-(1,1-dimethylethyl)-1-(1H-inden-1-yl)-1,1-dimethyl-；N-[1H-inden-1-yl(dimethyl)silyl]-2-methylpropan-2-amine
• CAS: 135610-16-1
• 化学式: C₁₅H₂₃NSi
• 分子量: 245.44
• InChiKey: FGVYHIWGQVBVAX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.93
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  氯化锆(IV) 、 1-<(tert-butylamino)dimethylsilyl>indene 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 以35%的产率得到二甲基硅基双(2-甲基-4-苯基茚定基)二氯化锆
  参考文献：
  名称：

  Dinuclear ansa zirconocene complexes containing a sandwich and a half-sandwich moiety as catalysts for the polymerization of ethylene

  摘要：

  Dinuclear ansa zirconocene complexes containing a half-sandwich and a sandwich moiety and their ligand precursors have been synthesized and characterized. After activation with methylalumoxane (MAO), these catalysts produce polyethylenes with bimodal molecular weight distributions in homogeneous and heterogeneous media. The catalyst performances and the polymer properties were compared with mono nuclear reference catalysts. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(02)01673-x
• 作为产物：
  描述：

  1-(chlorodimethylsilyl)indene 、 lithium tert-butylamide 以 正己烷 为溶剂， 以70%的产率得到1-<(tert-butylamino)dimethylsilyl>indene
  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

• Di‐ and Trivalent Ytterbium Complexes Containing Linked Amino‐ and Amidocyclopentadienyl Ligands
  作者：Alexander T. Trifonov、Thomas P. Spaniol、Jun Okuda

  DOI：10.1002/ejic.200390122

  日期：2003.3

  equivalents of potassium 1,2-diphenylethenide in THF, followed by reaction with [YbI2(THF)2] at 60 °C, gave the trivalent ytterbium ate complex [K(DME)][Yb(η5:η1-C5H3tBu-3)SiMe2NtBu}2]. A single crystal X-ray diffraction study of this complex shows polymeric chains consisting of trivalent ytterbocene units with two chelating amidocyclopentadienyl ligands coordinated to potassium ions. Metalation of the aminoindene

  室温下，氨基环戊二烯 (C5Me4H)SiMe2NHR（R = Et、烯丙基、nPr、tBu）与 [YbI2(THF)2] 在 THF 中存在两当量的 1,2-二苯基乙烯化钾的反应得到抗磁性半-夹心复合物 [Yb(η5-C5Me4SiMe2NHR)Ln(μ-I)]2 (L = THF, n = 2, L = DME, n = 1)。叔丁基酰胺衍生物 [Yb(η5-C5Me4SiMe2NHtBu)(THF)2(μ-I)]2 通过 X 射线结构分析表征为含有非螯合氨基环戊二烯基配体的双核复合物。氨基环戊二烯 (C5H4tBu)SiMe2NHtBu 在 THF 中用两当量的 1,2-二苯基乙烯化钾去质子化，然后与 [YbI2(THF)2] 在 60 °C 下反应，得到三价镱酸盐络合物 [K(DME)][ Yb(η5:η1-C5H3tBu-3)SiMe2NtBu}2]。该复合物的单晶 X 射线衍
• Single-Component Polymerization Catalysts for Ethylene and Styrene:  Synthesis, Characterization, and Reactivity of Alkyl and Hydrido Yttrium Complexes Containing a Linked Amido−Cyclopentadienyl Ligand
  作者：Kai C. Hultzsch、Peter Voth、Klaus Beckerle、Thomas P. Spaniol、Jun Okuda

  DOI：10.1021/om990583p

  日期：2000.2.1

  formation of the tetramethylcyclopentadienyl complexes Y(η5-C5Me4H)N(SiMe2CH2SiMe3)(R)}(CH2SiMe3)(THF)x (x = 0, 1). The dimeric hydrido complexes [Y(η5:η1-C5Me4SiMe2NCMe2R)(THF)(μ-H)]2 are prepared in good yields by hydrogenolysis of the corresponding alkyl complexes. Variable-temperature 1H, 13C, 29Si, and 89Y NMR spectroscopic data show that the hydrido complexes retain their dimeric structure in solution

  钇烷基配合物Y（η 5：η 1 -C 5我4森达2 NCMe 2 R）（CH 2森达3）（THF）（R =甲基，乙基）和Y（η 5：η 1 -C 9 ħ 6 SiMe 2 NCMe 3）（CH 2 SiMe 3）（THF）可以通过Y（CH 2 SiMe 3）3（THF）2与氨基官能化的环戊二烯或茚之间的σ键复分解反应高收率地制备。Y的结构（η 5：η 1单晶X射线衍射表明，-C 5 Me 4 SiMe 2 NCMe 2 Et）（CH 2 SiMe 3）（THF）为三足钢琴凳。Y（CH 2 SiMe 3）3（THF）2与三齿连接的酰胺基-环戊二烯基配体（C 5 Me 4 H）SiMe 2 NHR（R = CH 2 CH 2 OMe，CH 2 CH 2 NMe 2，CH 2 CH 2 CH 2 OMe，CMe 2CH 2 OME），其包含一个额外的供体部位，结果在硅-环戊二烯基键的裂解和四甲基环戊二烯的形成配合物Y（η
• Synthese, Charakterisierung und Polymerisationseigenschaften verbrückter Halbsandwichkomplexe des Titans, Zirconiums und Hafniums; Die Molekülstruktur von [C13H8-SiMe2-NtBu]ZrCl2
  作者：Helmut G. Alt、Klaus Föttinger、Wolfgang Milius

  DOI：10.1016/s0022-328x(98)00527-0

  日期：1999.1

  The synthesis of new ansa halfsandwich complexes of the type [Cp#-SiMe2-NtBu]MCl2 (Cp#=C13H8, C9H6, C5H4, C5H3tBu; M=Zr, Hf) as catalyst precursors for the polymerization of ethylene is described. The complexes were characterized by 1H-, 13C-, 29Si-, 15N- and 14N-NMR spectroscopy. From [C13H8-SiMe2-NtBu]ZrCl2 an X-ray structure was obtained. The activities of the catalysts and the properties of the

  [Cp ＃ -SiMe 2 -N t Bu] MCl 2（Cp ＃ = C 13 H 8，C 9 H 6，C 5 H 4，C 5 H 3 t Bu; M描述了作为乙烯聚合的催化剂前体的＝ Zr，Hf）。该复合物通过1 H-，13 C-，29 Si-，15 N-和14 N-NMR光谱表征。从[C 13 H 8 -SiMe 2得到-N t Bu] ZrCl 2的X射线结构。研究了催化剂的活性和聚合物的性能。讨论了催化剂结构对聚合行为的影响。
• 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.