[η1:η3-tert-butyl(dimethylfluorenylsilyl)amido]dimethyl titanium | 154283-79-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: [η1:η3-tert-butyl(dimethylfluorenylsilyl)amido]dimethyl titanium
• 英文别名: (tert-butylamino)dimethylfluorenylsilane；9-t-BuN(H)SiMe2-fluorene；9H-Fluorene, 9-[(t-butylamino)dimethylsilyl]-；N-[9H-fluoren-9-yl(dimethyl)silyl]-2-methylpropan-2-amine
• CAS: 154283-79-1
• 化学式: C₁₉H₂₅NSi
• 分子量: 295.5
• InChiKey: PWADFJWZRARIIZ-UHFFFAOYSA-N

物化性质

• 沸点：
  368.9±32.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.93
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.37
• 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：

  ZrCl₄(Et₂O)2 、 [η1:η3-tert-butyl(dimethylfluorenylsilyl)amido]dimethyl titanium 在 n-butyllithium 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 以50%的产率得到[η(1):η(5)-tert-butyl(dimethylfluorenylsilyl)amido]dichloro(diethyl ether)zirconium
  参考文献：
  名称：

  含连接的酰胺基-氟烯基配体的锆配合物的合成与表征

  摘要：

  Zirconium complexes containing an amido-fluorenyl ligand bridged by a dimethylsilylene group, C(13)H(8)SiMe(2)NCMe(3), have been synthesized. The dichloro complexes Zr(eta(5):eta(1)-C13H8-SiMe(2)NCMe(3))Cl-2(L) (L = THF, Et(2)O) were prepared by reacting ZrCl(4)L(2) with Li-2[C13H8-SiMe(2)NCMe(3)] and characterized as labile mono(solvent) adducts. Reaction with MeMgCl gives the thermally sensitive dimethyl complex Zr(eta(5):eta(1)-C(13)H(8)SiMe(2)NCMe(3))Me(2)(THF), whereas solvent-free dialkyl derivatives Zr(eta(5):eta(1)-C(13)H(8)SiMe(2)NCMe(3))Ph(2) and Zr(eta(5):eta(1)-C13H8-SiMe(2)NCMe(3))(CH(2)SiMe(3) )2, all under preservation of the chelate structure, are obtained with PhMgCl and Me(3)SiCH(2)MgCl, respectively. Variable-temperature H-1 NMR spectroscopic data reveal a sterically congested ligand sphere around the zirconium atom which is confirmed by a single-crystal X-ray diffraction study in the case of the bis(trimethylsilylmethyl) derivative. The substituted fluorenyl ligand is pentahapto-bonded with some variation of the zirconium-ring carbon bond lengths. The amido nitrogen is trigonal planar as a result of significant pi-donatian to the zirconium. The two (trimethylsilyl)methyl groups do not appear to be strongly distorted despite being bound to a 12-electron d(0) center but give rise to a conformation in which the repulsion between the trimethylsilyl and the tert-butyl groups is minimized. This compound crystallizes from pentane in the monoclinic space group P2(1)/n with a = 9.326(3), b = 16.806(5), and c = 19.638(6) Angstrom, beta = 93.23(2)degrees, V = 3073(2) Angstrom(3), Z = 4,R = 0.0308, wR(2) = 0.079.

  DOI：

  10.1021/om00002a028
• 作为产物：
  描述：

  芴 在 正丁基锂 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 8.0h， 生成 [η1:η3-tert-butyl(dimethylfluorenylsilyl)amido]dimethyl titanium
  参考文献：
  名称：

  Stereospecific polymerization of propylene with group 4 ansa-fluorenylamidodimethyl complexes

  摘要：

  Group 4 [eta(1):eta(3)-tert-butyl(dimethylfluorenylsilyl)amido]dimethyl complexes [t-BuNSiMe(2)Flu]MMe2 (M = Ti, 1; Zr, 2; Hf, 3) were synthesized in a one-pot synthesis starting from the ligand, MeLi and MCl4 (M = Ti, Zr, Hf), respectively. The structures of these complexes were determined by X-ray crystallography and the results obtained revealed that the fluorenyl ligand coordinates to center metal in a eta(3)-manner irrespective of center metal employed. Propylene polymerization was conducted at 0 or 20 degrees C in toluene by 1-3 combined with dried methylaluminoxane (MAO), which was prepared from the toluene solutions of MAO by removing free trialkylaluminiums, and HNMe2PhB(C6F5)(4) in the presence of triisobutylaluminium. The 1-dried MAO system gave the polymer with syndiotactic triad (rr) of 63% at 0 degrees C, whereas 2 and 3 did not give any polymer in the same conditions. The 2-dried MAO system gave the polymer with the highest syndiotacticity (rr = 97%) at 20 degrees C, although the activity was low. The 3-dried MAO system did not give any polymer even at 20 degrees C. When HNMe2PhB(C6F5)(4) was used in place of dried MAO at 20 degrees C, 1 gave almost atactic polymer, while 2 and 3 gave highly syndiotactic one (rr > 90%). These results indicate that the catalytic performance strongly depended on the center metal of the ansa-fluorenylamidodimethyl complexes as well as cocatalysts employed. (c) 2005 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2005.08.027

文献信息

• 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。
• Syntheses and Structures of Homoleptic Lanthanide Complexes with Chelating <i>o</i>-Dimethylaminobenzyl Ligands:  Key Precursors in Lanthanide Chemistry
  作者：Sjoerd Harder

  DOI：10.1021/om049327p

  日期：2005.1.1

  e2N-benzyl)Y·(THF) (7; 85% crystalline yield), shows a monomeric crystal structure with allylic coordination of the fluorenyl ring and bidentate coordination of the benzyl ligand. This complex was successfully hydrogenated with molecular H2 (10 bar) to yield the dimer [(9-t-BuNSiMe2-fluorenyl)YH·(THF)2]2 (8; 84% crystalline yield), in which the fluorenyl part of the ligand is bound to Y only in η1-fashion

  的反应ø -Me 2 N-C 6 H ^ 4 CH 2与YCLķ 3在THF中得到（直径： -Me 2 N-C 6 H ^ 4 CH 2）3 Y（5-Y ）中的浅黄色结晶板的形式（59％收率）。晶体结构显示与Y结合的三个二齿苄基配体，其具有棱柱形配位球。类似地制备La类似物（5-La）（41％的结晶产率），并且与5-Y同构，但显示出苄基配体与较大金属的更广泛的多全键结合（短的芳基-La相互作用）。尝试从o -Me 3 Si-C 6 H 4 CH 2 K和LaCl 3合成（o -Me 3 Si-C 6 H 4 CH 2）3 La出乎意料地得到[（o -Me 3 Si-C 6 H 4 CH 2）4的La - ] [李+ ·（THF）4 ]（32％产率结晶）时，Li的源+离子是不纯ö -Me 3的Si-C 6 H ^ 4 CH 2 K.晶体结构的测定揭示了（ø -Me 3的Si-C 6 H ^ 4
• Stereospecific polymerization of propylene with group 4 ansa-fluorenylamidodimethyl complexes
  作者：Kei Nishii、Hideaki Hagihara、Tomiki Ikeda、Munetaka Akita、Takeshi Shiono

  DOI：10.1016/j.jorganchem.2005.08.027

  日期：2006.1

  Group 4 [eta(1):eta(3)-tert-butyl(dimethylfluorenylsilyl)amido]dimethyl complexes [t-BuNSiMe(2)Flu]MMe2 (M = Ti, 1; Zr, 2; Hf, 3) were synthesized in a one-pot synthesis starting from the ligand, MeLi and MCl4 (M = Ti, Zr, Hf), respectively. The structures of these complexes were determined by X-ray crystallography and the results obtained revealed that the fluorenyl ligand coordinates to center metal in a eta(3)-manner irrespective of center metal employed. Propylene polymerization was conducted at 0 or 20 degrees C in toluene by 1-3 combined with dried methylaluminoxane (MAO), which was prepared from the toluene solutions of MAO by removing free trialkylaluminiums, and HNMe2PhB(C6F5)(4) in the presence of triisobutylaluminium. The 1-dried MAO system gave the polymer with syndiotactic triad (rr) of 63% at 0 degrees C, whereas 2 and 3 did not give any polymer in the same conditions. The 2-dried MAO system gave the polymer with the highest syndiotacticity (rr = 97%) at 20 degrees C, although the activity was low. The 3-dried MAO system did not give any polymer even at 20 degrees C. When HNMe2PhB(C6F5)(4) was used in place of dried MAO at 20 degrees C, 1 gave almost atactic polymer, while 2 and 3 gave highly syndiotactic one (rr > 90%). These results indicate that the catalytic performance strongly depended on the center metal of the ansa-fluorenylamidodimethyl complexes as well as cocatalysts employed. (c) 2005 Elsevier B. V. All rights reserved.
• Synthesis and Characterization of Zirconium Complexes Containing a Linked Amido-Fluorenyl Ligand
  作者：Jun Okuda、Florian J. Schattenmann、Sigrid Wocadlo、Werner Massa

  DOI：10.1021/om00002a028

  日期：1995.2

  Zirconium complexes containing an amido-fluorenyl ligand bridged by a dimethylsilylene group, C(13)H(8)SiMe(2)NCMe(3), have been synthesized. The dichloro complexes Zr(eta(5):eta(1)-C13H8-SiMe(2)NCMe(3))Cl-2(L) (L = THF, Et(2)O) were prepared by reacting ZrCl(4)L(2) with Li-2[C13H8-SiMe(2)NCMe(3)] and characterized as labile mono(solvent) adducts. Reaction with MeMgCl gives the thermally sensitive dimethyl complex Zr(eta(5):eta(1)-C(13)H(8)SiMe(2)NCMe(3))Me(2)(THF), whereas solvent-free dialkyl derivatives Zr(eta(5):eta(1)-C(13)H(8)SiMe(2)NCMe(3))Ph(2) and Zr(eta(5):eta(1)-C13H8-SiMe(2)NCMe(3))(CH(2)SiMe(3) )2, all under preservation of the chelate structure, are obtained with PhMgCl and Me(3)SiCH(2)MgCl, respectively. Variable-temperature H-1 NMR spectroscopic data reveal a sterically congested ligand sphere around the zirconium atom which is confirmed by a single-crystal X-ray diffraction study in the case of the bis(trimethylsilylmethyl) derivative. The substituted fluorenyl ligand is pentahapto-bonded with some variation of the zirconium-ring carbon bond lengths. The amido nitrogen is trigonal planar as a result of significant pi-donatian to the zirconium. The two (trimethylsilyl)methyl groups do not appear to be strongly distorted despite being bound to a 12-electron d(0) center but give rise to a conformation in which the repulsion between the trimethylsilyl and the tert-butyl groups is minimized. This compound crystallizes from pentane in the monoclinic space group P2(1)/n with a = 9.326(3), b = 16.806(5), and c = 19.638(6) Angstrom, beta = 93.23(2)degrees, V = 3073(2) Angstrom(3), Z = 4,R = 0.0308, wR(2) = 0.079.