dichlorobis(1,2-dimethylcyclopentadienyl)zirconium(IV) | 119445-91-9

• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: dichlorobis(1,2-dimethylcyclopentadienyl)zirconium(IV)
• 英文别名: bis(1,2-dimethylcyclopentadienyl)zirconoceneCl2；[(η(5)-1,2-dimethylcyclopentadienyl)2ZrCl2]；(1,2-Me2C5H3)2ZrCl2；(Cp-1,2-Me2)2ZrCl2；bis(1,2-dimethylcyclopentadienyl)zirconium dichloride；1,5-Dimethylcyclopenta-1,3-diene;zirconium(4+);dichloride；1,5-dimethylcyclopenta-1,3-diene;zirconium(4+);dichloride
• CAS: 119445-91-9
• 化学式: C₁₄H₁₈Cl₂Zr
• 分子量: 348.427
• InChiKey: LYIFUDYXUORMPY-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -1.95
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  dichlorobis(1,2-dimethylcyclopentadienyl)zirconium(IV) 、 (三甲基硅基)甲基氯化镁 以 乙醚 、 二氯甲烷 为溶剂， 以24%的产率得到chlorobis(1,2-dimethylcyclopentadienyl)(trimethylsilylmethyl)zirconium(IV)
  参考文献：
  名称：

  Metal-Alkyl Group Effects on the Thermodynamic Stability and Stereochemical Mobility of B(C₆F₅)₃-Derived Zr and Hf Metallocenium Ion-Pairs

  摘要：

  This paper reports significant dependence of ion-pair formation energetics and stereomutation rates upon the metal-bound alkyl substituent (R) and the solvent dielectric constant in the metallocenium series (1,2-Me2Cp)(2)MR+ MeB(C6F5)(3)(-) where R = Me, (CH2Bu)-Bu-t, CH2TMS, CH(TMS)(2), and M = Zr and Hf, as determined by reaction titration calorimetry and dynamic NMR spectroscopy. For the ion-pair forming reaction, (1,2 Me2Cp)(2)M(R)Me + B(C6F5)(3) --> (1,2-Me2Cp)(2)MR+ MeB(C6F5)(3)(-), enthalpies in toluene solution at 25 degreesC for M = Zr and R = Me, CH2TMS, and CH(TMS)(2) are -24.6(0.8), -22.6(1.0), and -59.2(1.4) kcal/mol, respectively. Corresponding values for M = Hf and R = Me and CH2TMS are -20.8(0.5) and -31.1(1.6) kcal/mol, respectively. DeltaH double dagger (reorg) values for the reorganization process that interchanges the ion-pair enantiotopic sites for M = Zr and R = Me, (CH2Bu)-Bu-t, CH2TMS, and CH(TMS)(2) are 22(1), 18(1), 17(1), and 9(2) kcal/mol, respectively. Corresponding DeltaH double dagger (reorg) values for M = Hf and R = Me, (CH2Bu)-Bu-t, and CH2TMS are >24, 12(3), and 15(2) kcal/mol, respectively. DeltaH double dagger (reorg) values are highest in low dielectric constant solvents such as C6D12 Activation parameters for beta -Me elimination in the complexes (1,2-Me2Cp)(2)(MCH2Bu+)-Bu-t MeB(C6F5)(3)(-) for M = Zr and Hf are found to be DeltaH double dagger (beta -Me) = 22.5(0.9) and 17.3(0.9) kcal/mol, and DeltaS double dagger (beta -Me) = 4.3(3.3) and -11.9(3.4) cal/mol(.)K, respectively.

  DOI：

  10.1021/ja000810a

文献信息

• Significant Zirconium−Alkyl Group Effects on Ion Pair Formation Thermodynamics and Structural Reorganization Dynamics in Zirconocenium Alkyls
  作者：Colin L. Beswick、Tobin J. Marks

  DOI：10.1021/om990274z

  日期：1999.6.1

  Substantial Zr−alkyl group (R) effects on ion pair thermodynamic stability as well as on ion pair solution structure and structural dynamics are reported in the [(1,2-Me2Cp)2ZrR]+[CH3B(C6F5)3]- series, where R = CH3, CH2C(CH3)3, CH2Si(CH3)3, and CH[Si(CH3)3]2. These quantitative results underscore the effects such R moieties are likely to play in group 4 metallocenemediated olefin polymerization catalysis

  在[（1,2-Me 2 Cp）2 ZrR] + [CH 3 B（C 6）中报告了大量的Zr-烷基（R）对离子对热力学稳定性以及离子对溶液结构和结构动力学的影响F 5）3 ] -系列，其中R = CH 3，CH 2 C（CH 3）3，CH 2 Si（CH 3）3和CH [Si（CH 3）3 ] 2。这些定量结果强调了这样的R部分可能在第4族茂金属介导的烯烃聚合催化中发挥的作用。
• Preparation and Characterization of Bis(cyclopentadienyl)zirconium(II) Complexes with a Tethered Olefin−Phosphine Ligand
  作者：Akiko Yamazaki、Yasushi Nishihara、Kiyohiko Nakajima、Ryuichiro Hara、Tamotsu Takahashi

  DOI：10.1021/om990103u

  日期：1999.8.1

  Unprecedented zirconium(II) complexes bearing tethered olefin−phosphine ligands were synthesized and characterized. The molecular structures of the newly synthesized complexes (η5-1,2-Me2C5H3)2Zr(CH2CHCH2CH2PPh2) (1c) and Cp2Zr(CH2CHCH2CH2CH2PPh2) (2a) were determined by single-crystal X-ray diffraction methods. The stability and reactivity of the series of complexes Cp2ZrCH2CH(CH2)nPR2} (n = 2, 3;

  合成并表征了前所未有的带有链状烯烃-膦配体的锆（II）配合物。新合成的复合物的分子结构（η 5 -1,2-我2 ç 5 ħ 3）2的Zr（CH 2 CHCH 2 CH 2 PPH 2）（1C）1和Cp 2 Zr的（CH 2 CHCH 2 CH 2 CH通过单晶X射线衍射法确定2 PPh 2）（2a）。系列配合物Cp 2 Zr CH的稳定性和反应性检验了2 CH（CH 2）n PR 2 }（n＝ 2，3； R ＝ Et，Ph）。配合物2a同时显示出足够的稳定性和高反应性。
• Cationic Alkylaluminum-Complexed Zirconocene Hydrides: NMR-Spectroscopic Identification, Crystallographic Structure Determination, and Interconversion with Other Zirconocene Cations
  作者：Steven M. Baldwin、John E. Bercaw、Lawrence M. Henling、Michael W. Day、Hans H. Brintzinger

  DOI：10.1021/ja1050428

  日期：2011.2.16

  The ansa-zirconocene complex rac-Me2Si(1-indenyl)(2)-ZrCl2 ((SBI)ZrCl2) reacts with diisobutylaluminum hydride and trityl tetrakis(perfluorophenyl)borate in hydrocarbon solutions to give the cation [(SBI)Zr(mu-H)(3)((AlBu2)-Bu-i)(2)](+), the identity of which is derived from NMR data and supported by a crystallographic structure determination. Analogous reactions proceed with many other zirconocene dichloride complexes. [(SBI)Zr(mu-H)(3)((AlBu2)-Bu-i)(2)](+) reacts reversibly with (ClAlBu2)-Bu-i to give the dichloro-bridged cation [(SBI)Zr(mu-Cl)(2)(AlBu2)-Bu-i](+). Reaction with AIMe(3) first leads to mixed-alkyl species [(SBI)Zr(mu-H)(3)(AIMe(x)(i)Bu(2-x))(2)](+) by exchange of alkyl groups between aluminum centers. At higher AlMe3/Zr ratios, [(SBI)Zr(mu-Me)(2)AlMe2](+), a constituent of methylalumoxane-activated catalyst systems, is formed in an equilibrium, in which the hydride cation [(SBI)Zr(mu-H)(3)(AIR(2))(2)](+) strongly predominates at comparable HAI(i)Bu(2) and AlMe3 concentrations, thus implicating the presence of this hydride cation in olefin polymerization catalyst systems.
• 1H-, 13C-NMR and ethylene polymerization studies of zirconocene/MAO catalysts: effect of the ligand structure on the formation of active intermediates and polymerization kinetics
  作者：Konstantin P Bryliakov、Nina V Semikolenova、Dmitrii V Yudaev、Vladimir A Zakharov、Hans H Brintzinger、Martin Ystenes、Erling Rytter、Evgenii P Talsi

  DOI：10.1016/s0022-328x(03)00443-1

  日期：2003.10

  Using H-1- and C-13-NMR spectroscopies, cationic intermediates formed by activation of L2ZrCl2 with methylaluminoxane (MAO) in toluene were monitored at Al/Zr ratios from 50 to 1000 (L-2 are various cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands). The following catalysts were studied: (Cp-R)(2)ZrCl2 (R = Me, 1,2-Me2, 1,2,3-Me-3, 1,2,4-Me-3, Me-4, Me-5, n-Bu, t-Bu), rac-ethanediyl(Ind)(2)ZrCl2, rac-Me2Si(Ind)(2)ZrCl2, rac-Me2Si(1-Ind-2-Me)(2)ZrCl2, rac-ethanediyl(1-Ind-4,5,6,7-H-4)(2)ZrCl2, (Ind-2Me)(2)ZrCl2, Me2C(CP)(Flu)ZrCl2, Me2C(Cp-3-Me)(Flu)ZrCl2 and Me2Si(Flu)(2)ZrCl2- Correlations between spectroscopic and ethene polymerization data for catalysts (Cp-R)(2)ZrCl2/MAO (R = H, Me, 1,2-Me-2, 1,2,3-Me-3, 1,2,4-Me-3, Me-4, Me-5, n -Bu, t-Bu) and rac-Me2Si(Ind)(2)ZrCl2 were established. The catalysts (Cp-R)(2)ZrCl2/AlMe3/CPh3+B(C6F5)(4)(-) (R= Me, 1,2-Me-2, 1,2,3-Me-3, 1,2,4-Me-3, Me-4, n -Bu, t -Bu) were also studied for comparison of spectroscopic and polymerization data with MAO-based systems. Complexes of type (Cp-R)(2)ZrMe+ <-- Me- -Al equivalent to MAO (IV) with different [Me-MAO](-) counteranions have been identified in the (Cp-R)(2)ZrCl2/MAO (R = H-Bu, t-Bu) systems at low Al/Zr ratios (50-200). At Al/Zr ratios of 500-1000, the complex [L2Zr(mu-Me)(2)AlMe2](+)[Me-MAO](-) (HI) dominates in all MAO-based reaction systems studied. Ethene polymerization activity strongly depends on the Al/Zr ratio (Al/Zr = 200 - 1000) for the systems (Cp-R)(2)ZrCl2/MAO (R = H, Me, n -Bu, t -Bu), while it is virtually constant in the same range of Al/Zr ratios for the catalytic systems (Cp-R)(2)ZrCl2/MAO (R = 1,2-Me-2, 1,2,3-Me-3, 1,2,4-Me-3, Me-4) and rac-Me2Si(Ind)(2)ZrCl2/MAO. The data obtained are interpreted on assumption that complex III is the main precursor of the active centers of polymerization in MAO-based systems. (C) 2003 Elsevier Science B.V. All rights reserved.
• Metal-Alkyl Group Effects on the Thermodynamic Stability and Stereochemical Mobility of B(C₆F₅)₃-Derived Zr and Hf Metallocenium Ion-Pairs
  作者：Colin L. Beswick、Tobin J. Marks

  DOI：10.1021/ja000810a

  日期：2000.10.1

  This paper reports significant dependence of ion-pair formation energetics and stereomutation rates upon the metal-bound alkyl substituent (R) and the solvent dielectric constant in the metallocenium series (1,2-Me2Cp)(2)MR+ MeB(C6F5)(3)(-) where R = Me, (CH2Bu)-Bu-t, CH2TMS, CH(TMS)(2), and M = Zr and Hf, as determined by reaction titration calorimetry and dynamic NMR spectroscopy. For the ion-pair forming reaction, (1,2 Me2Cp)(2)M(R)Me + B(C6F5)(3) --> (1,2-Me2Cp)(2)MR+ MeB(C6F5)(3)(-), enthalpies in toluene solution at 25 degreesC for M = Zr and R = Me, CH2TMS, and CH(TMS)(2) are -24.6(0.8), -22.6(1.0), and -59.2(1.4) kcal/mol, respectively. Corresponding values for M = Hf and R = Me and CH2TMS are -20.8(0.5) and -31.1(1.6) kcal/mol, respectively. DeltaH double dagger (reorg) values for the reorganization process that interchanges the ion-pair enantiotopic sites for M = Zr and R = Me, (CH2Bu)-Bu-t, CH2TMS, and CH(TMS)(2) are 22(1), 18(1), 17(1), and 9(2) kcal/mol, respectively. Corresponding DeltaH double dagger (reorg) values for M = Hf and R = Me, (CH2Bu)-Bu-t, and CH2TMS are >24, 12(3), and 15(2) kcal/mol, respectively. DeltaH double dagger (reorg) values are highest in low dielectric constant solvents such as C6D12 Activation parameters for beta -Me elimination in the complexes (1,2-Me2Cp)(2)(MCH2Bu+)-Bu-t MeB(C6F5)(3)(-) for M = Zr and Hf are found to be DeltaH double dagger (beta -Me) = 22.5(0.9) and 17.3(0.9) kcal/mol, and DeltaS double dagger (beta -Me) = 4.3(3.3) and -11.9(3.4) cal/mol(.)K, respectively.