dichloro(N,N'-o-phenylenebis(3,5-di-tert-butylsalicylideneiminato))zirconium(IV) | 910921-33-4

• 英文名称: dichloro(N,N'-o-phenylenebis(3,5-di-tert-butylsalicylideneiminato))zirconium(IV)
• 英文别名: ZrCl2(N,N'-o-phenylene-bis(3,5-di-tert-butyl-salicylidene-imine(-2H))；ZrCl2(N,N'-o-phenylenebis(3,5-di-tert-butylsalicylideneiminate))；[ZrCl2(N,N'-phenylenebis(3,5-di-tert-butylsalicylideneiminate))]
• CAS: 910921-33-4；653601-18-4
• 化学式: C₃₆H₄₆Cl₂N₂O₂Zr
• 分子量: 700.903
• InChiKey: HNWKYLAJNRFQBO-BUAHPEKYSA-J

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：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  sodium tetracarbonyl cobaltate 、 dichloro(N,N'-o-phenylenebis(3,5-di-tert-butylsalicylideneiminato))zirconium(IV) 以 四氢呋喃 为溶剂， 以86 %的产率得到(salphenZr)₂Cl₃Co(CO)₄
  参考文献：
  名称：

  氯桥二聚 SalphenZr(IV) 钴酸盐催化剂释放可生物降解 PHA 的无碱羰基化聚合潜力†

  摘要：

  聚（3-羟基链烷酸酯）（PHA）是一类有前途的可生物降解聚合物，其性能可与传统石油基聚合物相媲美。尽管如此，由于缺乏有效且经济可行的催化系统，PHA 的广泛商业化受到阻碍，从而削弱了其与不可生物降解聚合物的竞争力。为了应对这一挑战，我们提出了一项新开发的氯桥二聚 Salphen 钴酸锆配合物的研究，用于通过环氧化物的羰基化聚合直接合成 PHA。该催化系统在温和的反应条件下表现出良好的活性，能够实现单体的完全转化以及对 PHA 形成的高达 92% 的选择性。通过细致的控制实验和机理研究，我们对聚合过程有了重要的了解。值得注意的是，我们的研究结果挑战了原位生成的β-内酯的顺序开环聚合作为主要途径的普遍观念。相反，我们证明聚合主要通过环氧化物和一氧化碳的直接共聚进行，揭示了一种独特且有效的 PHA 合成机制。

  DOI：

  10.1002/cjoc.202300343
• 作为产物：
  描述：

  ZrCl2(N,N'-o-phenylene-bis(3,5-di-tert-butyl-salicylidene-imine(-2H)) 以 further solvent(s) 为溶剂， 生成 dichloro(N,N'-o-phenylenebis(3,5-di-tert-butylsalicylideneiminato))zirconium(IV)
  参考文献：
  名称：

  A zirconium dichloro complex supported by an ancillary stereorigid tetradentate bis(phenoxo-imino) Schiff-base-donor ligand: Evidence for a conformational equilibrium between two solution stereoisomers

  摘要：

  Reaction of the dilithium salt of the Schiff-base N,N'-o-phenylene-bis(3,5-di-tert-butyl-salicylidene-imine) ((t)Bu(4)salophenH(2)) with 1 equiv. of ZrCl4(THF)(2) in toluene at -78 degrees C affords the dichloro complex ZrCl2[C6H4-1,2-{N=CH-(3,5-(Bu2C6H2)-Bu-t-2-O)}(2)], isolated as a mixture of the C-2v-(3a) and C-2-(3b) symmetry isomers. Thermodynamic and kinetic parameters for the equilibrium between 3a and 3b have been determined and studied by H-1 NMR spectroscopy. Reactions of ZrCl2[C6H4-1,2-{N=CH-(3,5-(Bu2C6H2)-Bu-t-2-O)}(2)] with alkylating reagents gave an intractable, unidentified mixture of products from which the NMR spectra in C6D6 solution are unusable. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2006.05.025

文献信息

• Salen-type zirconium complexes with a labile coordination site and a robust skeleton: crystal structure of [(t-Bu4-salen)ZrCl2(H2O)]
  作者：Mei Wang、Hongjun Zhu、Deguang Huang、Kun Jin、Changneng Chen、Licheng Sun

  DOI：10.1016/j.jorganchem.2004.01.014

  日期：2004.4

  of association and disassociation of H2O molecule in [LZrCl2(H2O)n] (n=0, 1) were studied in solution (CDCl3) by 1H NMR spectroscopy. The crystal and molecular structure of [1(H2O)] was determined by X-ray diffraction analysis, which revealed that a herringbone supramolecular assembly was constructed in the crystalline state of [1(H2O)], stacked by the intermolecular hydrogen bonds between the OH group

  的LZrCl治疗2（L = Ñ，Ñ ' -ethylenebis（3,5-二-叔-butylsalicylideneiminato）（1），Ñ，Ñ ' - Ö -phenylenebis（3,5-二-叔-butylsalicylideneiminato）（2） ），这是一种有效的乙烯低聚催化剂前体，在甲苯中加入1.5当量的水可制得H 2 O配位的Salen型锆配合物[LZrCl 2（H 2 O）]。H 2 O的含量和温度对H 2缔合与解离平衡的影响通过1 H NMR光谱研究了溶液（CDCl 3）中[LZrCl 2（H 2 O）n ]（n = 0，1）中的O分子。的晶体和分子结构[ 1（H 2 O）]通过X射线衍射分析，其显示，人字形超分子组装体中的[结晶状态，构建测定1（H 2 O）]，通过分子间堆叠配位的H 2 O的OH基团与氯化物配体之一之间的氢键。
• Ethylene oligomerization by salen-type zirconium complexes to low-carbon linear α-olefins
  作者：Mei Wang、Hongjun Zhu、Kun Jin、Dong Dai、Licheng Sun

  DOI：10.1016/s0021-9517(03)00306-3

  日期：2003.12

  activities in ethylene oligomerization under a pressure of 1.0–1.8 MPa at 150 °C in toluene. The main products are C4–C10 olefins with good selectivity to linear α-olefins. The turnover frequency (TOF) of catalyst system Zr(salen)Cl2·THF/Et2AlCl, under a pressure of 1.8 MPa and in an Al/Zr molar ratio of 300, was 4.93×104 h−1 with a satisfactory selectivity to C4–C10 olefins (89%), and linear α-olefins accounted

  通过使用ZrCl 4和四齿Schiff碱配体的钠盐制备了一系列的salen锆配合物。与Et 2 AlCl结合，它们在乙烯低聚中（在150°C下于1.0–1.8 MPa的压力下于150°C的甲苯中）表现出中等至高的催化活性。主要产品是对直链α-烯烃具有良好选择性的C 4 -C 10烯烃。催化剂体系Zr（salen）Cl 2 ·THF / Et 2 AlCl在1.8 MPa的压力下和Al / Zr摩尔比为300时的周转频率（TOF）为4.93×10 4  h -1，令人满意。对C 4 –C 10的选择性烯烃（89％）和直链α-烯烃占95％。研究了配体对乙烯低聚的空间和共轭作用，以及助催化剂，Al / Zr摩尔比，反应温度，乙烯压力和催化剂寿命的影响。
• Preparation and structures of 6- and 7-coordinate salen-type zirconium complexes and their catalytic properties for oligomerization of ethylene
  作者：Hongjun Zhu、Mei Wang、Chengbing Ma、Bo Li、Changneng Chen、Licheng Sun

  DOI：10.1016/j.jorganchem.2005.05.027

  日期：2005.9

  A series of salen-type zirconium complexes of the general formula LZrCl2 (L = N,N '-ethylenebis(salicylideneiminate), 3a; N,N '-ethylenebis(3,5-di-tert -butylsalicylideneiminate), 3b; N,N '-ethylenebis(5-methoxysalicylidenciminate), 3e; N,N '-o-phethylenebis(5-chlorosalicylideneiminate), 3d; N,N '-ethylenebis(5-nitrosalicylideneiminate), 3e; N,N '-o-phenylenebis(salicylideneiminate), 4a; N,N '-o-phenylenebis(3,5-di-tert-butylsalicylideneiminate), 4b; N,N '-o-phenylenebis(5-methoxysalicylideneiminate), 4c; N,N '-o-phenylenebis(5-chloro-salicylideneiminate), 4d) were prepared. The crystal structures of 6- and 7-coordinate zirconium complexes 4b and [4b center dot OCMe2] were determined by X-ray crystallography, which reveals that a salen-type zirconium complex possesses a labile coordination site on the Zr center with a relatively stable framework and that the coordination and the dissociation of O-donor molecules occur readily at this site. The catalytic properties of 3(a-e) and 4(a-d) were studied for ethylene oligomerization in combination with Et2AlCl as co-catalyst. Complex 3c featuring a methoxy-substituted salen ligand displayed higher activity than its analogous precursors having chloro and nitro groups as substituents. The catalytic reactions by 3(a-e) and 4(a-d) gave C-4-C-10 olefins and low-carbon linear (alpha-olefins in good selectivity. (c) 2005 Elsevier B.V. All rights reserved.