[(2-((2,6-diisopropylphenyl)amido)-4-((2,6-diisopropylphenyl)imino)-2-pentene)ZnOAc]2 | 215808-46-1

• 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: [(2-((2,6-diisopropylphenyl)amido)-4-((2,6-diisopropylphenyl)imino)-2-pentene)ZnOAc]2
• 英文别名: [(2-((2,6-diisopropylphenyl)amido)-4-((2,6-diisopropylphenyl)imino)-2-penteneato)Zn(μ,η2-OAc)]2；[Zn(O2CCH3)(N(2,6-di(isopropyl)phenyl)C(CH3)CHC(CH3)N(2,6-di(isopropyl)phenyl))]2
• CAS: 215808-46-1
• 化学式: C₆₂H₈₈N₄O₄Zn₂
• 分子量: 1084.19
• InChiKey: PLJMIBLEPJOAAA-MNWBCHASSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 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：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [(2-((2,6-diisopropylphenyl)amido)-4-((2,6-diisopropylphenyl)imino)-2-pentene)ZnOAc]2 以 氘代甲苯 为溶剂， 生成 [(2-((2,6-diisopropylphenyl)amido)-4-((2,6-diisopropylphenyl)imino)-2-penteneato)ZnOAc]
  参考文献：
  名称：

  Mechanism of the Alternating Copolymerization of Epoxides and CO₂ Using β-Diiminate Zinc Catalysts:  Evidence for a Bimetallic Epoxide Enchainment

  摘要：

  A series of zinc beta-diiminate (BDI) complexes and their solid-state structures, solution dynamics, and copolymerization behavior with CO2 and cyclohexene oxide (CHO) are reported. Stoichiometric reactions of the copolymerization initiation steps show that zinc alkoxide and bis(trimethylsilyl)amido complexes insert CO2, whereas zinc acetates react with CHO. [(BDl-2)ZnOMe](2) [(BDI-2) = 2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-pentene] and (BDI-1)(ZnOPr)-Pr-i [(BDI-1) = 2-((2,6-diisopropylphenyl)amido)-4-((2,6-diisopropylphenyl)imino)-2-pentene] react with CO2 to form [(BDI-2)Zn(mu-OMe) (mu,eta(2)-O2COMe)Zn(BDI-2)] and [(BDI-1)Zn(mu-eta(2)-(O2COPr)-Pr-i)](2), respectively. (BDI-2)ZnN(SiMe3)(2) inserts CO2 and eliminates trimethylsilyl isocyanate to give [(BDI-2)Zn(mu-OSiMe3)](2). [(BDI-7)Zn(mu-OAc)](2) [(BDI-7) = 3-cyano-2-((2,6-diethylphenyl) amido)-4-((2,6-diethylphenyl)imino)-2-pentene) reacts with 1.0 equiv of CHO to yield [(BDI-7)Zn(mu,eta(2)-OAc)-(mu,eta(1)-OCyOAc)Zn(BDI-7)]. Under typical polymerization conditions, rate studies on the copolymerization exhibit no dependence in [CO2], a first-order dependence in [CHO], and orders in [Zn]tot ranging from 1.0 to 1.8 for [(BDI)ZnOAc] complexes. The copolymerizations of CHO (1.98 M in toluene) and 300 Psi CO2 at 50 degreesC using [(BDI-1)ZnOAc] and [(BDI-2)ZnOAc] show orders in [Zn](tot) of 1.73 +/- 0.06 and 1.02 +/- 0.03, respectively. We propose that two zinc complexes are involved in the transition state of the epoxide ring-opening event.

  DOI：

  10.1021/ja030085e
• 作为产物：
  描述：

  (2-((2,6-diisopropylphenyl)amido)-4-((2,6-diisopropylphenyl)imino)-2-pentene)ZnN(SiMe3)2 、 溶剂黄146 以 甲苯 为溶剂， 以34%的产率得到[(2-((2,6-diisopropylphenyl)amido)-4-((2,6-diisopropylphenyl)imino)-2-pentene)ZnOAc]2
  参考文献：
  名称：

  Single-Site β-Diiminate Zinc Catalysts for the Alternating Copolymerization of CO₂ and Epoxides:  Catalyst Synthesis and Unprecedented Polymerization Activity

  摘要：

  Synthetic routes to zinc ss -diiminate complexes are reported. The synthesis of 11 ss -diimine [(BDI)H] ligands, with varying N-aryl substituents and bridging structures, is described. These ligands are converted to (BDI)ZnX complexes (X = OAc. Et. N(SiMe3)(2), Br, Cl, OH, OMe, (OPr)-Pr-i). X-ray structural data revealed that all zinc complexes examined exist as mu -X-bridged dimers in the solid state, with the exception of the zinc ethyl and amido complexes which were monomeric. Complexes of the form (BDI)ZnOR (R = alkyl, acyl) and (BDI)ZnN(SiMe3)(2) are highly active catalysts for the alternating copolymerization of epoxides and CO2. Copolymerizations of cyclohexene oxide (CHO) and CO2 with (BDI-1)ZnX [(BDI-1) = 2-((2,6-diisopropylphenyl)amido)-4-((2,6-diisopropylphenyl)imino)-2-pentene)] and (BDI-2)ZnX [(BDI-2) = 2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-pentene)], where X = OAc, Et, N(SiMe3)(2), Br, Cl, OH, OMe, (OPr)-Pr-i, were attempted at 50 degreesC and 100 Psi CO2. Complexes with X = OAc, N(SiMe3)(2), OMe, (OPr)-Pr-i all produced polycarbonate by the alternated insertion of CHO and CO2 with similar catalytic activities, comparable molecular weights, and narrow molecular weight distributions (MWD similar to 1.1), indicating the copolymerizations are living. Furthermore, ligand effects were shown to dramatically influence the polymerization activity as minor steric changes accelerated or terminated the polymerization activity.

  DOI：

  10.1021/ja003850n

文献信息

• Polymerization of Lactide with Zinc and Magnesium β-Diiminate Complexes:  Stereocontrol and Mechanism
  作者：Bradley M. Chamberlain、Ming Cheng、David R. Moore、Tina M. Ovitt、Emil B. Lobkovsky、Geoffrey W. Coates

  DOI：10.1021/ja003851f

  日期：2001.4.1

  alkoxides based upon a beta-diiminate ligand framework has been prepared. [(BDI-1)ZnO(i)Pr](2) [(BDI-1) = 2-((2,6-diisopropylphenyl)amido)-4-((2,6-diisopropylphenyl)imino)-2-pentene] exhibited the highest activity and stereoselectivity of the zinc complexes studied for the polymerization of rac- and meso-lactide to poly(lactic acid) (PLA). [(BDI-1)ZnO(i)()Pr](2) polymerized (S,S)-lactide to isotactic

  已经制备了一系列基于 β-二亚胺配体框架的锌 (II) 和镁 (II) 醇盐。[(BDI-1)ZnO(i)Pr](2) [(BDI-1) = 2-((2,6-二异丙基苯基)酰胺基)-4-((2,6-二异丙基苯基)亚氨基)-2-戊烯] 在研究外消旋和内消旋丙交酯聚合成聚乳酸 (PLA) 的锌配合物中表现出最高的活性和立体选择性。[(BDI-1)ZnO(i)()Pr](2) 将 (S,S)-丙交酯聚合成全同立构 PLA，没有单体差向异构化，外消旋丙交酯变成异同立构 PLA (P(r) = 0.94 at 0° C)，以及内消旋丙交酯到间规 PLA（P(r) = 0.76 在 0 摄氏度）。除了数均分子量与转化率曲线和单体与催化剂比率的线性性质外，聚合反应是活跃的，这由分离的聚合物的窄多分散性证明。β-二亚胺配体上的取代基对聚合过程产生显着影响，影响立体选择性程度和聚合速率。[(BDI-1)ZnO(i)Pr](2)
• Structure and reactivity of mono- and dinuclear diiminate zinc alkyl complexes
  作者：Scott D Allen、David R Moore、Emil B Lobkovsky、Geoffrey W Coates

  DOI：10.1016/s0022-328x(03)00544-8

  日期：2003.10

  The synthesis, structure and reactivity of several diiminate ligands are presented. The syntheses of five representative beta-diiminate (BDI) zinc alkyl complexes and one beta-oxo-delta-diiminate (BODDI) zinc alkyl are described. BDI ligands with varying backbone and N-aryl substituents display different solid state structures. [(BDI)ZnR] are synthesized by the reaction of (BDI)H with ZnR, in quantitative yield. Previously reported (BDI-1)ZnEt is a three-coordinate monomer in the solid state whereas [(BDI-3)ZnEt](infinity) [(BDI-3) = 2-((2,6-diisopropylphenyl)amido)-3-cyano-4-((2,6-diisopropylphenyl)imino-2-pentene] and [(BDI-4)ZnEt](infinity) [(BDI-4) = 2-((2,6-diethylphenyl)amido)-3-cyano-4-((2,6-diethylphenyl)imino-2-pentene] form one dimensional coordination polymers. The bimetallic complex [(BODDI-1)(ZnEt)(2)] [(BODDI-1) = 2,6-bis((2,6-diisopropylphenyl)amido)-2,5-heptadien-4-one] is prepared through the reaction of (BODDI-1)H-2 with two equivalents ZnEt2. Both [(BDI)ZnEt] and [(BODDI)ZnEt] complexes react with acetic acid to give the acetate complexes in moderate to high yields, offering a superior synthetic route to these complexes. [(BDI)ZnR] [BDI=(BDI-3) or 1,1,1-trifluoro-2-((2,6-diisopropylphenyl)amido)-4-((2,6-diethylphenyl)imino-2-pentene), (BDI-5)] complexes react with MeOH to produce [(BDI)Zn(mu-OMe)}(2)Zn(mu-OMe)(2)] in moderate yields. The molecular structures of [(BDI-3)ZnEt], [(BDI-4)ZnEt], [(BODDI-1)(ZnEt)(2)], [(BODDI-1)Zn-2(mu-OAc)(2)], [(BDI-3)Zn(mu-OMe)}(2)Zn(mu-OMe)(2)] and [(BDI-5)Zn(mu-OMe)}(2)Zn(mu-OMe)2] have been determined by X-ray diffraction. (C) 2003 Elsevier B.V. All rights reserved.