monozirconium(IV) monochloride mono(phenylmethanide) | 24356-03-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: monozirconium(IV) monochloride mono(phenylmethanide)
• 英文别名: dibenzylzirconium dichloride；bis-benzyl-zirconium(IV) dichloride；Zr(CH2Ph)2Cl2；ZrBn₂Cl₂
• CAS: 24356-03-4
• 化学式: C₁₄H₁₄Cl₂Zr
• 分子量: 344.395
• InChiKey: MGYZYLGWXRQUPL-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  4.85
• 重原子数：
  17.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  monozirconium(IV) monochloride mono(phenylmethanide) 、 2,3,4,5,6-pentafluoro-N-[2-[2-[2-(2,3,4,5,6-pentafluoroanilino)ethoxy]ethoxy]ethyl]aniline 以 not given 为溶剂， 以90%的产率得到dichlorozirconium(2+);(2,3,4,5,6-pentafluorophenyl)-[2-[2-[2-(2,3,4,5,6-pentafluorophenyl)azanidylethoxy]ethoxy]ethyl]azanide
  参考文献：
  名称：

  Zirconium Complexes of Fluorinated Aryl Diamides

  摘要：

  The reaction of excess (ArNHLi)-N-F with (ICH2CH2OCH2)(2) affords the new diamines ((ArNHCH2CH2OCH2)-N-F)2 (1, Ar-F = C6F5; 2, Ar-F = 3,5-C6H3(CF3)(2)) in moderate yield. Direct protonolysis of Zr(CH2Ph)(n)Cl4-n (n = 2-4) or Zr[N(SiMe3)(2)](n)Cl4-n (n = 2, 3) with 1 or 2 (1 equiv) affords the zirconium complexes Zr((ArNCH2CH2OCH2)-N-F)(2)(X)(Y) (Ar-F = C6F5: 3, X = Y = Cl; 4, X = N(SiMe3)(2,) Y = Cl; 5, X = Cl, Y = CH2Ph; 6, X = Y = CH2Ph. Ar-F = 3,5-C6H3(CF3)(2): 7, X = Y = Cl; 8, X = Y = CH2Ph). The structures of 1, 4, 5, and 7 were established by X-ray crystalIography with the zirconium complexes 4, 5, and 7 all adopting a monocapped trigonal bipyramidal geometry in the solid state. However, in solution, these complexes display higher symmetry due to rapid ligand rearrangement. The silylamido complex 4 shows restricted rotation of the C6F5 rings in solution (DeltaG(double dagger) = 49 +/- 3 kJ mol(-1)). Abstraction of a benzyl group from 6 by B(C6F5)(3) affords {Zr [CH2OCH2CH2N(C6F5)](2)(CH2Ph)}(+){(PhCH2)B(C6F5)(3)} - (9) This complex shows evidence for eta (2)-benzyl coordination and does not polymerize ethylene at room temperature. Treatment of 3 with excess MAO (500 equiv) and ethylene(1 atm, 50 degreesC) affords polyethylene at a modest rate (3.2 kg mol(-1) Zr h(-1)).

  DOI：

  10.1021/om0006559
• 作为产物：
  描述：

  zirconium tetrachloride bis(tetrahydrofuran) complex 、 以 四氢呋喃 为溶剂， 反应 5.0h， 生成 monozirconium(IV) monochloride mono(phenylmethanide)
  参考文献：
  名称：

  Generation of Ti^II Alkyne Trimerization Catalysts in the Absence of Strong Metal Reductants

  摘要：

  Low-valent Ti-II species have typically been synthesized by the reaction of Ti-IV halides with strong metal reductants. Herein we report that Ti-II species can be generated simply by reacting Ti-IV imido complexes with 2 equiv of alkyne, yielding a metallacycle that can reductively eliminate pyrrole while liberating Ti-II. In order to probe the generality of this process, Ti-II-catalyzed alkyne trimerization reactions were carried out with a diverse range of Ti-IV precatalysts.

  DOI：

  10.1021/acs.organomet.7b00096

文献信息

• [EN] BRIDGED BI-AROMATIC LIGANDS AND OLEFIN POLYMERIZATION CATALYSTS PREPARED THEREFROM<br/>[FR] LIGANDS BI-AROMATIQUES PONTÉS ET CATALYSEURS DE POLYMÉRISATION D'OLÉFINES PRÉPARÉS À PARTIR DE CEUX-CI
  申请人：UNIVATION TECH LLC

  公开号：WO2016172097A1

  公开（公告）日：2016-10-27

  Disclosed are novel bridged bi-aromatic phenol ligands and transition metal catalyst compounds derived therefrom. Also disclosed are methods of making the ligands and transition metal compounds, and polymerization processes utilizing the transition metal compounds for the production of olefin polymers.

  揭示了新型的桥接双芳香酚配体和由此衍生的过渡金属催化剂化合物。还揭示了制备这些配体和过渡金属化合物的方法，以及利用这些过渡金属化合物进行聚合反应生产烯烃聚合物的工艺。
• [EN] SYNTHESIS OF BENZYLOXYPHENOXY PHENOL LIGANDS<br/>[FR] SYNTHÈSE DE LIGANDS BENZYLOXYPHÉNOXY PHÉNOLIQUES
  申请人：UNIVATION TECH LLC

  公开号：WO2018129235A1

  公开（公告）日：2018-07-12

  Synthetic methods for the preparation of ligands and metal-ligand complexes are disclosed.

  揭示了用于配体和金属配体络合物制备的合成方法。
• [EN] BIS(AMINOPHENYLPHENOL) LIGANDS AND TRANSITION METAL COMPOUNDS PREPARED THEREFROM<br/>[FR] LIGANDS DE BIS(AMINOPHÉNYLPHÉNOL) ET COMPOSÉS DE MÉTAUX DE TRANSITION PRÉPARÉS À PARTIR DE CEUX-CI
  申请人：UNIVATION TECH LLC

  公开号：WO2016176138A1

  公开（公告）日：2016-11-03

  Disclosed are novel bis(aminophenylphenol) ligands and transition metal compounds derived therefrom. Also disclosed are methods of making the ligands and transition metal compounds.

  揭示了新型的双(氨基苯酚基)配体和由此衍生的过渡金属化合物。还揭示了制备这些配体和过渡金属化合物的方法。
• Cationic Zirconium Dialkyl and Alkyl Complexes Supported by DAC (Deprotonated 4,13-Diaza-18-crown-6) Ligation
  作者：Lawrence Lee、David J. Berg、Gordon W. Bushnell

  DOI：10.1021/om961027n

  日期：1997.6.1

  trans-1a. Reaction of Zr(CH2Ph)2Cl2 with H2DAC, followed by treatment with LiR (2 equiv), gives cis-Zr(DAC)R2 (R = CH2SiMe3, cis-1b; R = CH2CMe3, cis-1c) exclusively. Alkyl abstraction from cis- or trans-1a using B(C6F5)3 (1 equiv) produces the stable cation [Zr(DAC)(CH2Ph)]+[B(CH2Ph)(C6F5)3]- (2a) as a yellow oil. NMR studies on 2a in CD2Cl2 show no evidence for η2-benzyl formation or anion coordination.

  报道了由DAC（去质子化的4,13-diaza-18-crown-6）连接支持的一系列中性和阳离子Zr烷基的合成，表征和反应性。H 2 DAC与Zr（CH 2 Ph）4的反应得到顺式-和反式-Zr（DAC）（CH 2 Ph）2（顺式/反式-1a）的1：4混合物。纯异构体在溶液中经历缓慢的顺-反异构化，以再生1：4的顺：反平衡混合物。X射线晶体学的结果汇报了顺式-和反式- 1A。Zr（CH 2 Ph）2 Cl 2与H 2 DAC反应，然后用LiR（2当量）处理，得到顺式-Zr（DAC）R 2（R = CH 2 SiMe 3，顺式-1b ; R = CH 2 CME 3，顺式- 1C）独占。使用B（C 6 F 5）3（1当量）从顺式或反式-1a烷基提取产生稳定的阳离子[Zr（DAC）（CH 2 Ph）] + [B（CH 2Ph）（C 6 F 5）3 ] -（2a）为黄色油。核磁共振研究2A在CD
• Preparation of octahydro- and tetrahydro-[1,10]phenanthroline zirconium and hafnium complexes for olefin polymerization
  作者：Eun Yeong Hwang、Geun Ho Park、Chun Sun Lee、Yi Young Kang、Junseong Lee、Bun Yeoul Lee

  DOI：10.1039/c4dt03683b

  日期：——

  A zirconium complex with an unusual binding mode was constructed from octahydro[1,10]phenanthroline, which is a potent catalyst for the production of wax-like low-molecular weight polyethylene (M_n: ∼5000).

  使用辛烷基[1,10]邻菲啰啉构建的锆配合物具有不寻常的结合方式，是一种有效的催化剂，可用于生产类似蜡的低分子量聚乙烯（Mn：∼5000）。