[(2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-penteneato)Zn(μ,η2-OAc)]2 | 369404-42-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: [(2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-penteneato)Zn(μ,η2-OAc)]2
• CAS: 369404-42-2
• 化学式: C₅₄H₇₂N₄O₄Zn₂
• 分子量: 971.97
• InChiKey: PVIDBAIRAYEOOR-HBIQXNNGSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 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-diethylphenyl)amino)-4-((2,6-diethylphenyl)imino)-2-pentene)Zn(μ-methoxy)]₂ 、 [(2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-penteneato)Zn(μ,η2-OAc)]2 以 甲苯 为溶剂， 以99%的产率得到
  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-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-penteneato)ZnEt 、 溶剂黄146 以 正己烷 为溶剂， 以85%的产率得到[(2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-penteneato)Zn(μ,η2-OAc)]2
  参考文献：
  名称：

  Structure and reactivity of mono- and dinuclear diiminate zinc alkyl complexes

  摘要：

  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.

  DOI：

  10.1016/s0022-328x(03)00544-8

文献信息

• Single-Site β-Diiminate Zinc Catalysts for the Alternating Copolymerization of CO₂ and Epoxides:  Catalyst Synthesis and Unprecedented Polymerization Activity
  作者：Ming Cheng、David R. Moore、Joseph J. Reczek、Bradley M. Chamberlain、Emil B. Lobkovsky、Geoffrey W. Coates

  DOI：10.1021/ja003850n

  日期：2001.9.1

  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.