[(CH3)2C(η(5)-C5H5)(fluorenyl)]Zr(CH3)][(CH3)B(C6F5)3] | 206852-64-4

• 英文名称: [(CH3)2C(η(5)-C5H5)(fluorenyl)]Zr(CH3)][(CH3)B(C6F5)3]
• 英文别名: [Me2C(fluorenyl)(Cp)ZrMe][MeB(C6F5)3]
• CAS: 206852-64-4
• 化学式: C₁₉H₃BF₁₅*C₂₂H₂₁Zr
• 分子量: 903.653
• InChiKey: XJBPZIUWZDQGGD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [(CH3)2C(η(5)-C5H5)(fluorenyl)]Zr(CH3)][(CH3)B(C6F5)3] 以 甲苯 为溶剂， 生成
  参考文献：
  名称：

  对单中心烯烃聚合过程的显着反阴离子效应。离子对结构和动力学与聚合活性、链转移和间选择性的相关性

  摘要：

  反阴离子对原型 C(s) 对称预催化剂 [Me(2)C(Cp)(Flu)]ZrMe(2) 对间规丙烯链化速率和立体化学的影响 (1; Cp = C(5)H(4) ); Flu = C(13)H(8), 芴基) 使用助催化剂 MAO (2), B(C(6)F(5))(3) (3)(,) B(2-C) 进行探测(6)F(5)C(6)F(4))(3) (4)(,) Ph(3)C(+)B(C(6)F(5))(4)(-) (5) 和 Ph(3)C(+)FAl(2-C(6)F(5)C(6)F(4))(3)(-) (6)，提供截然不同的结构和离子配对特征。1 与 3 反应得到 [Me(2)C(Cp)(Flu)]ZrMe(+) MeB(C(6)F(5))(3)(-) (7)。在 4 的情况下，该反应导致形成微甲基双核非对映异构体 [([Me(2)C(Cp)(Flu)]ZrMe)(2)(micro-Me)](+)

  DOI：

  10.1021/ja036288k
• 作为产物：
  描述：

  trityl tris(perfluorophenyl)fluoroborate 、 (η5-C5H4)CMe2-η5-(C13H8)ZrMe2 以 甲苯 为溶剂， 生成 [(CH3)2C(η(5)-C5H5)(fluorenyl)]Zr(CH3)][(CH3)B(C6F5)3]
  参考文献：
  名称：

  立体特异性烯烃聚合的新型单核和多核全氟芳基金属酸盐助催化剂

  摘要：

  已经合成了用于茂金属介导的烯烃聚合的单核和多核全氟芳基硼酸酯，-铝酸盐和-没食子酸酯助催化剂，作为已知的全氟芳基准金属助催化剂的三苯甲基氟化物加合物。使用这些物种与C s对称的预催化剂[Me 2 C（Cp）（芴基）] ZrMe 2进行的丙烯聚合实验表明，聚合活性，产物聚合物间同立构性以及相对[ m ]和[ mm ]均具有明显的抗衡离子依赖性。立体误差丰富，多核全氟芳基助催化剂与中性类似物相比，均匀地增强了产品聚合物的立体规则性。

  DOI：

  10.1021/om0341698

文献信息

• Stereochemical nonrigidity in metallocenium ions
  作者：A.R. Siedle、R.A. Newmark

  DOI：10.1016/0022-328x(95)00114-6

  日期：1995.7

  Dynamic NMR spectroscopy of the MeB(C6F53− salts of a series of ring-substituted zirconium- and hafnium-containing metallocenium ions, exemplified by (RCp)2ZrCH3+, reveals two exchange processes. One, having the lower free energy of activation, involves shift of the CH3 group from one lateral equatorial orbital to the other. The second results from exchange between the metal-CH3 and B-CH3 groups. Effects

  MEB的动态NMR光谱（C 6 ˚F 5 3 -一系列环取代的锆和含铪茂金属离子，由（RCP）例举的盐2 ZrCH 3 +，其中说明了两个交换过程的一种，具有较低。活化的自由能涉及CH 3基团从一个赤道侧向轨道转移到另一侧，第二个结果来自金属CH 3和B-CH 3基团之间的交换，并讨论了结构变化对交换壁垒的影响和相关性茂金属离子催化的烯烃聚合。
• Sterically Encumbered (Perfluoroaryl) Borane and Aluminate Cocatalysts for Tuning Cation−Anion Ion Pair Structure and Reactivity in Metallocene Polymerization Processes. A Synthetic, Structural, and Polymerization Study
  作者：You-Xian (Eugene) Chen、Matthew V. Metz、Liting Li、Charlotte L. Stern、Tobin J. Marks

  DOI：10.1021/ja973769t

  日期：1998.7.1

  The synthesis and dialkyl abstraction chemistry as well as the unusual cocatalytic characteristics in metallocene-mediated polymerization of two distinctive borane and aluminate cocatalysts tris(2,2',2"-nonafluorobiphenyl)borane (PBB) and triphenyl carbenium tris(2,2',2"-nonafluorobiphenyl)fluoroaluminate, (Ph(3)C(+)PBA(-)) are reported. Reaction of PBB with Cp'2ThMe2 (Cp' = eta(5)-C5Me5), CGCZrMe(2) (CGC = Me2-Si(eta(5)-Me4C5)('BuN)), and Cp'MMe3 (M = Zr, Hf) cleanly affords base-free cationic complexes Cp'2ThMe+MePBB- (1), CGCZrMe(+)MePBB(-) (5), and Cp'MMe2+MePBB- (M = Zr, 7; Hf, 8), in case of CGCTiMe(2) and dimethyl zirconocenes, mu-methyl dinuclear cationic complexes [(CGeTiMe)(2)(mu-Me)](+) MePBB- (6) and [(L2ZrMe)(2)(mu-Me)]+MePBB- (L = eta(5)-C5H5 (CP), 2; eta(5)-1,2-Me2C5H3 (CP''), 3; Cp', 4; L-2 = Me2Si(Ind)(2), Ind = eta(5)-C9H6, 9; L-2 = Me2C(Flu)(Cp), Flu = eta(5)-C13H8, 10) are formed. A similar reaction with Ph3C+PBA- results in the corresponding complexes CGCZrCH(3)(+)PBA(-) (M = Zr, 19; Ti, 20) and L(2)ZrCH(3)(+)PBA(-) (L = Cp, 15b; Cp", 16; eta(5)-1,3-(SiMe2)(2)C5H3, 17; Cp', 18; L-2 = Me2Si(Ind)(2), 21; L-2 = Me2C(Flu)(Cp), 22). Two dinuclear complexes 3 and 13 ([Me2C(Flu)(Cp)Zr(C6F5)](2)(mu-F)+MeB(C6F5)(3)(-)) derived from borane PBB and B(C6F5)(3), respectively, and three other PBA(-)-based monomeric complexes 14 (Ph(3)C(+)PBA(-)), 19, and 21 have been characterized by X-ray diffraction, and these determinations allow detailed analysis of the ion pairing in the solid state. In combination with solution dynamic NMR, all data indicate MePBB--cation interactions to be considerably weaker than those involving MeB(C6F5)(3)(-), while the strongly ion-paired chiral PBA(-) converts previously enantiomeric cations into pairs of diastereomers. As revealed by dynamic H-1 NMR studies, ion pair reorganization/symmetrization in 5 is significantly more rapid than in the MeB(C6F5)(3)(-) analogue, suggesting much looser ion pairing in 5. On the other hand, PBA- racemization is a rapid process (e.g., Delta G double dagger(58 degrees C) = 16.9(2) kcal/mol for 16), while cation-PBA(-) ion pairs have higher barriers for ion pair symmetrization than in analogous fluoroaryl borates. Dinuclear complexes 2 and 3 initiate efficient polymerization of methyl methacrylate (MMA) to produce syndiotactic poly(methyl methacrylate) (PMMA), while 9 produces highly isotactic PMMA, and sterically more accessible complexes 6 and 10 exhibit no activity.For olefin polymerization and copolymerization, PBB-derived cationic complexes, both monomeric and dinuclear, generally exhibit higher catalytic activity and comonomer incorporation levels than the MeB(C6F5)(3)(-) analogues, with CGC catalysts exhibiting the greatest activity contrasts. On the other hand, PBA(-)-derived complexes exhibit a remarkable sensitivity of olefin polymerization characteristics and ion pairing to ancillary ligand bulk, with activity differences of up to 10(6)-fold observed. Ln regard to stereospecific polymerization, PBA--derived chiral complex 21 produces highly isotactic polypropylene while B(C6F5)(4)(-)- derived analogue produces isotactic polypropylene with lower isotacticity under similar conditions. Microstructure analyses of poly(ethylene-co-1-hexene) samples indicate that PBB enhances comonomer incorporation randomness.
• Strong Ion Pairing Effects on Single-Site Olefin Polymerization:  Mechanistic Insights in Syndiospecific Propylene Enchainment
  作者：Ming-Chou Chen、Tobin J. Marks

  DOI：10.1021/ja011558p

  日期：2001.11.1