[(2-((2,6-diethylphenyl)amino)-4-((2,6-diethylphenyl)imino)-2-pentene)Zn(μ-methoxy)]₂ | 224966-59-0

• 英文名称: [(2-((2,6-diethylphenyl)amino)-4-((2,6-diethylphenyl)imino)-2-pentene)Zn(μ-methoxy)]₂
• 英文别名: [(^Et,EtNacNac)Zn(μ-OMe)]₂；[(2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-penteneato)Zn(μ-OMe)]2；[(2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-pentene)Zn(OCH3)]2
• CAS: 224966-59-0
• 化学式: C₅₂H₇₂N₄O₂Zn₂
• 分子量: 915.949
• InChiKey: WFYUHEUJDNXGAZ-HBIQXNNGSA-N

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：
  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：

  [(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-pentene)Zn(isopropoxide)] 以 氘代苯 为溶剂， 生成 [(2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-pentene)Zn]2(OCH3)(OC3H7)
  参考文献：
  名称：

  Single-Site β-Diiminate Zinc Catalysts for the Ring-Opening Polymerization of β-Butyrolactone and β-Valerolactone to Poly(3-hydroxyalkanoates)

  摘要：

  Polymerization of beta-butyrolactone (BBL) and beta-valerolactone (BVL) using the zinc alkoxide initiator (BDI-1)(ZnOPr)-Pr-l [(BDI-1) = 2-((2,6-diisopropylphenyl)amido)-4-((2,6-diisopropylphenyl)imino)-2-pentene] proceeds very rapidly under mild conditions to produce poly(3-hydroxybutyrate) (PHB) and poly(3-hyd roxyvalerate) (PHV), respectively. For the monomer-to-initiator ratio 200:1, PHB number-average molecular weights (M-n) are proportional to conversion throughout the reaction and polydispersity indices (PDIs) are narrow, consistent with a living polymerization. Higher monomer-to-initiator ratios can be used to achieve high molecular weight PHB (Mn > 100 000). End-group analysis verifies that the polymerization of BBL follows a coordination-insertion mechanism, where complexes of the form (BDI-1)ZnOCH(Me)CH2CO2R are the active species. Variable temperature NMR experiments show that (BDI-1)ZnO/Pr is monomeric in benzene-d(6) solution. In contrast, (BDI-2)ZnO/Pr [(BDI-2) = 2-((2,6-diethylphenyl)amido)-4-((2,6-diethy[phenyl)imino)-2-pentene] is a poor initiator at room temperature because it prefers to form a bis-mu-isopropoxide dimer in solution. According to kinetic studies, propagation by (BDI-1)ZnO/Pr is first order in both monomer as well as (BDI-1)ZnO/Pr concentration. These results lead us to propose a monometallic active species. Several results suggest that elimination side reactions are slowly catalyzed by zinc alkoxides, leading to degradation of the polymer.

  DOI：

  10.1021/ja020978r
• 作为产物：
  描述：

  (2,6-diethylphenyl)NHC(CH3)CHC(CH3)N(2,6-diethylphenyl) 以 甲醇 、 甲苯 为溶剂， 生成 [(2-((2,6-diethylphenyl)amino)-4-((2,6-diethylphenyl)imino)-2-pentene)Zn(μ-methoxy)]₂
  参考文献：
  名称：

  The Ethylsulfinate Ligand:  A Highly Efficient Initiating Group for the Zinc β-Diiminate Catalyzed Copolymerization Reaction of CO₂ and Epoxides

  摘要：

  The quantitative synthesis of a series of new zinc(II) sulfinate complexes (4a-e) by insertion of SO2 into zinc-ethyl bonds of beta-diiminate complexes ((ArN= C(CH3)CH=(CH3)CNAr)Zn(O(S=O)Et); Ar = 2,6-diisopropylphenyl (4a), 2,6-diethylphenyl (4b), 2-ethyl-6-isopropylphenyl (4c), 2,6-diphenylphenyl (4d), 2,q-bis(4-tert-butylphenyl)phenyl (4e)) is described. X-ray structure analysis reveals a dinuclear, mu-ethylsulfinate-bridged structure for 4a in the solid state, which in solution exists in an equilibrium with the mononuclear species. The easily accessible complexes 4a-c are highly active catalysts for the alternating copolymerization Of CO2 and cyclohexene oxide, leading to products with narrow molecular weight distributions.

  DOI：

  10.1021/om020734f

文献信息

• Syntheses of transition metal methoxysiloxides
  作者：Casseday P. Richers、Jeffery A. Bertke、Thomas B. Rauchfuss

  DOI：10.1039/c6dt04205h

  日期：——

  three methods for the preparation of methoxysiloxide complexes, a rare class of complexes of relevance to room temperature vulcanization (RTV) of polysiloxanes. The salt metathesis reaction involves the use of the recently described reagent NaOSi(OMe)2Me with various metal chlorides to give Cp*2Ti[OSi(OMe)2Me](OMe), (Me,MeN2N)NiOSi(OMe)2Me, (IPr)CuOSi(OMe)2Me, and (triphos)CoOSi(OMe)2Me (Cp* = C5Me5, triphos

  该论文描述了三种制备甲氧基氧化硅配合物的方法，这是一种与聚硅氧烷的室温硫化（RTV）有关的稀有配合物。盐复分解反应涉及使用最近描述的试剂NaOSi（OMe）2 Me与各种金属氯化物来生成Cp * 2 Ti [OSi（OMe）2 Me]（OMe），（Me，Me N 2 N）NiOSi（ OMe）2 Me，（IPr）CuOSi（OMe）2 Me和（triphOS）CoOSi（OMe）2 Me（Cp * = C 5 Me 5，三光子= Me（CH 2 PPh 2）3）。几个尝试反应得到的甲醇络合物代替，即归因于κ的中间性的通路2 -OSi（OME）2我种。二醇Cp * 2 Zr（OH）2与过量的（MeO）3 SiMe反应，得到Cp * 2 Zr [OSi（OMe）2 Me] 2。相反，亲核性较低的Cp * 2 Ti（OH）2是不反应的。制备甲氧基氧化硅配合物的第三种途径涉及Cp * 2 M（O）（py）与（MeO）3
• 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.
• Mechanism of the Alternating Copolymerization of Epoxides and CO₂ Using <i>β</i>-Diiminate Zinc Catalysts:  Evidence for a Bimetallic Epoxide Enchainment
  作者：David R. Moore、Ming Cheng、Emil B. Lobkovsky、Geoffrey W. Coates

  DOI：10.1021/ja030085e

  日期：2003.10.1

  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.