(η⁵-cyclopentadienyl)trichlorohafnium dimethoxyethane | 129174-25-0

• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: (η⁵-cyclopentadienyl)trichlorohafnium dimethoxyethane
• 英文别名: CpHfCl₃*DME；Hf(η-C5H5)Cl3 * DME；[Hf(η-C5H5)Cl3*1,2-dimethoxyethane]；hafnium (cyclopentadienyl)(Cl3)*CH3OCH2CH2OCH3；[Hf(η5-C5H5)Cl3*DME]；cyclopenta-1,3-diene;1,2-dimethoxyethane;hafnium(4+);trichloride
• CAS: 129174-25-0
• 化学式: C₄H₁₀O₂*C₅H₅Cl₃Hf
• 分子量: 440.066
• InChiKey: BCXCUFPATBRKFS-UHFFFAOYSA-K

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：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  Zr(Me2Si(η-C5H4)2)(η-C5H5)Cl 、 (η⁵-cyclopentadienyl)trichlorohafnium dimethoxyethane 以 甲苯 为溶剂， 以52.7%的产率得到(η-C5H5)ZrCl2(μ-η-C5H4-(SiMe2)-η-C5H4)HfCl2(η-C5H5)
  参考文献：
  名称：

  Synthesis and catalytic properties of ansa-binuclear metallocenes of the Group IV transition metals

  摘要：

  The new ansa-bridged mono- and bi-nuclear Group IV metallocenes, {Zr[X(eta-C5H4)(2)](eta-C5H5)Cl} (where, X = SiMe(2) (1), CMe(2)CMe(2) (2)), {[(eta-C5H5)HfCl2][mu-eta-C5H4-(SiMe(2))-eta-C5H4][(eta-C5H5)HfCl2]} (3). {[(eta-C5H5)ZrCl2][mu-eta-C5H4(SiMe(2)CH(2)CH(2)SiMe(2))-eta-C5H4][(eta-C5H5)ZrCl2]} (4), {[(eta-C5H5)ZrCl2][mu-eta-C5H4-(SiMe(2))-eta-C9H6][(eta-C5H5)ZrCl2]} (5), {[(eta-C5H5)ZrCl2][mu-eta-C9H6-(SiMe(2))-eta-C9H6][(eta-C5H5)ZrCl2]} (6), {[(eta-C5H5)ZrCl2][mu-eta-C5H4-(SiMe(2))-eta-C5H4][(eta-C5H5)MCl(2)]}, M = Hf (7) or Ti (8), {[(eta-C5H5)ZrCl2][mu-eta-C5H4-(SiMe(2))-eta-C5H4][(eta-C(5)Me(5))TiCl2]} (9) and {[(eta-C5H5)ZrCl2][mu-eta-C5H4(SiMe(2))-eta-C5H4][TiCl3]} (10) an described. These compounds in the presence of methylaluminoxane are catalysts for the polymerisation of ethene and propene.

  DOI：

  10.1016/0022-328x(96)06198-0

文献信息

• Metallocene Compounds Having Appended Lewis Acids and Polymerization Therewith
  申请人：ExxonMobil Chemical Patents Inc.

  公开号：US20200071349A1

  公开（公告）日：2020-03-05

  This invention relates to metallocene compounds represented by the formula: catalyst systems comprising said metallocene compound and an activator or a reaction product of the metallocene compound with the at least one activator, and polymerization processes using such metallocene compounds and activators, where Cp a and Cp b are optionally-substituted cyclopentadienyl rings; A is bridging group; q is zero or 1; Q is O, O(CR 3 R 4 ) m , (CR 3 R 4 ) m O, or (CR 3 R 4 ) m ; m is 0 to 18; Z is (CR 3 R 4 ) 2 ; LA is a Lewis acid; M is a transition metal; X 1 and X 2 are independently R 5 or OR 5 ; R 1 and R 2 are independently selected from optionally-substituted hydrocarbyl groups; R 3 and R 4 are independently selected from the group consisting of H, halogen, and an optionally-substituted hydrocarbyl group; and R 5 is alkyl, aryl, perfluoroalkyl, or perfluoroaryl.

  这项发明涉及由以下公式表示的茂金属化合物： 包括所述茂金属化合物和活化剂或所述茂金属化合物与至少一个活化剂的反应产物的催化剂体系，以及使用这种茂金属化合物和活化剂的聚合过程，其中Cp a 和Cp b 是可选择取代的环戊二烯基环；A是桥连基；q为零或1；Q为O、O(CR 3 R 4 ) m 、(CR 3 R 4 ) m O或(CR 3 R 4 ) m ；m为0至18；Z为(CR 3 R 4 ) 2 ；LA为路易斯酸；M为过渡金属；X 1 和X 2 独立地为R 5 或OR 5 ；R 1 和R 2 独立地选自可选择取代的烃基团；R 3 和R 4 独立地选自H、卤素和可选择取代的烃基团的群；R 5 为烷基、芳基、全氟烷基或全氟芳基。
• Alkylidenverbrückte dissymmetrische zweikernige Metallocenkomplexe als Katalysatoren für die Ethylenpolymerisation
  作者：Matthias Deppner、Ralf Burger、Helmut G. Alt

  DOI：10.1016/j.jorganchem.2003.11.043

  日期：2004.4

  dissymmetric alkylidene bridged dinuclear metallocene complexes of titanium, zirconium and hafnium and some of the corresponding mononuclear reference complexes. The influence of structural parameters on the polymerization behaviour of the MAO activated complexes is systematically investigated for homogeneous ethylene polymerization. The dinuclear catalysts show higher polymerization activities than a mixture

  描述了钛，锆和ha的不对称亚烷基桥连的双核茂金属配合物以及一些相应的单核参比配合物的合成。对于均相乙烯聚合，系统地研究了结构参数对MAO活化配合物聚合行为的影响。与由类似的单核参比催化剂组成的混合物相比，双核催化剂显示出更高的聚合活性。由双核配合物获得的聚乙烯比由单核配合物生产的聚乙烯具有更高的多分散性。
• Synthesis and reactivity of new mixed dicyclopentadienyl Group 4 metal complexes with the doubly bridged bis(dimethylsilanediyl)-cyclopentadiene-(η5-cyclopentadienyl) ligand
  作者：Roberto Gómez-Garcı́a、Pascual Royo

  DOI：10.1016/s0022-328x(99)00111-4

  日期：1999.6

  The monocyclopentadienyl titanium complex [Ti(C5H4)(SiMe2)2(η5-C5H3)} Cl3] 3 and the dichloro mixed dicyclopentadienyl Group 4 metal complexes [M(η5-C5R5)(C5H4)(SiMe2)2(η5-C5H3)} Cl2] (R=H; M=Ti 4, Zr 5, Hf 6; R=Me; M=Ti 7) containing the doubly bridged bis(dimethylsilanediyl)-cyclopentadiene-(η5-cyclopentadienyl) ligand were prepared in high yields by reaction of the monolithium salt Li[(C5H4)(SiMe2)2(C5H3)]

  单环戊二烯基钛配合物[钛（C 5 H ^ 4）（森达2）2（η 5 -C 5 H ^ 3）}氯3 ] 3和二氯二环戊二烯基混合4种族金属配合物[M（η 5 -C 5 - [R 5）（C 5 H ^ 4）（森达2）2（η 5 -C 5 H ^ 3）}氯2 ]（R = H; M =的Ti 4，Zr的5，HF 6 ; R =甲基; M =钛7）含有双重桥连的双（二甲基硅烷二）-cyclopentadiene-（η 5 -环戊二烯基）配位体进行了以高收率由单锂盐的反应而制备的Li [（C 5 H ^ 4）（森达2）2（C 5 H ^ 3）]分别具有等摩尔量的TiCl 4或单环戊二烯基络合物[Cp'MCl 3 ]。与得到氯代各种烷基化剂的氯络合物的反应[M（η 5 -C 5 H ^ 5）（C 5 H ^ 4）（森达2）2（η 5 -C 5 H ^ 3）} CLR]（M = Ti中R =我8，等9
• New mono- and bi-nuclear ansa-metallocenes of zirconium and hafnium as catalysts for the polymerisation of ethene and propene
  作者：Gary M. Diamond、Alexander N. Chernega、Philip Mountford、Malcolm L. H. Green

  DOI：10.1039/dt9960000921

  日期：——

  2)C9H6}Zr(η-C5Me5)Cl2], [M(C5H4CMe2C9H7)}(η-C5H5)Cl2](M = Zr or Hf) and [ZrC5H4CMe2(C9H7}(η-C 5H5)Me2] have been prepared and characterised. The activity of the metallocenes as cocatalysts for the polymerisation of ethene and propene has been evaluated.

  新的柄-metallocenes [M 我2 C（η-C 5 H ^ 4）（η 2 -C 9 ħ 6）}（η-C 5 H ^ 5）CL] [M = Zr的（晶体结构），或者，铪]，[M （CH 2）5 C（η-C 5 H ^ 4）（η 2 -C 9 ħ 6）}（η-C 5 H ^ 5）CL]·0.5C 6 H ^ 5我[M = Zr的（晶体结构）或Hf]，[Zr的我2 C（η-C 5 H ^ 4）（η 3 -C 13ħ 8）}（η-C 5 H ^ 5）CL]（晶体结构），[M 我2 C（η-C 5 H ^ 4）2 }（η-C 5 H ^ 5）CL] [M = Zr或HF（晶体结构）]，[X 2（η-C 5 H ^ 5）M C 5 ħ 4（CME 2）C 9 H ^ 6）} M *（η-C 5 H ^ 5）X 2 }]（X = Cl，M，M * = Zr，Zr; Hf，Hf; Zr，Hf;或Hf，Zr;
• tert-Butylsilylcyclopentadienyl Group 4 metal complexes
  作者：Regine Wolfgramm、Cristina Ramos、Pascual Royo、Maurizio Lanfranchi、Maria Angela Pellinghelli、Antonio Tiripicchio

  DOI：10.1016/s0020-1693(02)01446-9

  日期：2003.4

  New Group 4 metal t-butyldimethylsilyleyclopentadienyl complexes [MCpCp'Cl-2] (Cp = eta(5)-C5H5 : Cp' = eta(5)'-C5H4SiMe2',Bu; M = Ti 4, Zr 5, Hf 6) were prepared by reaction of 1 equiv. of the lithium (2) and thallium (3) salts of t-butyldimethylsilylcyclopentadiene I with the monocyclopentadienyl complexes [MCpCl3. DME] (M = Zr, Hf) and [TiCpCl3], respectively, A similar reaction using ZrCl4(THF)2 and HfCl4 with 2 equiv. of the lithium salt 2 gave the symmetric [MCp2Cl2] (M = Zr 7, Hf8) rnetallocenes. Alkylation of these compounds with 2 equiv. of MgRCl (R = Me. CH2Ph) and Li(CH2CMe2Ph) afforded the dialkyl complexes [MCpCp'R-2] (R = Me, M = Zr 9, Hf 10: R = CH2Ph. M = Ti 11. Zr 12. Hf 13). [ZrCp2(CH2Ph):] 14 and [ZrCpCp'(CH2CMe2Ph)(2)] 17, A Similar reaction of 5 with 1 equiv. of Mg(CH2Ph)Cl gave the monobenzyl compound [ZrCpCp'Cl(CH2Ph)] (15), Hydrolysis of 15 with a stoichiometric amount of water afforded the dinuclear mu-oxo compound [(ZrCpCp'Cl)(2)(mu-O)] (16). All of the new complexes reported were characterized by elemental analysis and H-1 and C-13 NMR spectroscopy and the molecular structures of 4 and 16 were determined by X-ray diffraction methods. Ethylene polymerization activities were measured for compounds 4-7. (C) 2002 Elsevier Science B.V. All rights reserved.