N,N'-bis(3-tert-butyl-5-nitrosalicylidene)-1,2-ethylenediimine | 849060-27-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: N,N'-bis(3-tert-butyl-5-nitrosalicylidene)-1,2-ethylenediimine
• 英文别名: [((t)Bu(NO2)salenH2]；2-Tert-butyl-6-[2-[(3-tert-butyl-2-hydroxy-5-nitrophenyl)methylideneamino]ethyliminomethyl]-4-nitrophenol
• CAS: 849060-27-1
• 化学式: C₂₄H₃₀N₄O₆
• 分子量: 470.525
• InChiKey: WWCXMEROYSHPOE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  34
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  157
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  N,N'-bis(3-tert-butyl-5-nitrosalicylidene)-1,2-ethylenediimine 、 氯化二乙基铝 以 甲苯 为溶剂， 以91%的产率得到[N,N'-bis(3-tert-butyl-5-nitrosalicylidene)-1,2-ethylenediimine]aluminum(III) chloride
  参考文献：
  名称：

  Aluminum Salen Complexes and Tetrabutylammonium Salts:  A Binary Catalytic System for Production of Polycarbonates from CO₂ and Cyclohexene Oxide

  摘要：

  A series of complexes of the form (salen)AIZ, where H(2)salen = N,N'-bis(salicylidene)-1,2-phenylenediimine and various other salen derivatives and Z = Et or Cl, have been synthesized. Several of these complexes have been characterized by X-ray crystallography. An investigation of the utilization of these aluminum derivatives along with both ionic and neutral bases as cocatalysts for the copolymerization of carbon dioxide and cyclohexene oxide has been conducted. By studying the reactivity of these complexes for this process as substituents on the diimine backbone and phenolate rings are altered, we have observed that aluminum prefers electron-withdrawing groups on the salen ligands, thereby producing an electrophilic metal center to be most active toward production of polycarbonates from CO2 and cyclohexene oxide. For example, the complex derived from H(2)salen = N,N'-bis-(3,5-di-tert-butylsalicylidene)-1,2-ethylenediimine is essentially inactive when compared to the analogous derivative containing nitro substituents in the 3-positions of the phenolate groups. This is to be contrasted with the catalytic activity observed for the (salen)CrX systems, where electron-donating salen ligands greatly enhanced the reactivity of these complexes for the coupling Of CO2 and epoxides. While (salen)AIZ complexes are capable of producing poly(cyclohexene oxide) carbonate with low amounts of polyether linkage along with small quantities of cyclic carbonate byproducts, their reactivities, covering a turnover frequency range of 5.2-35.4 mol of epoxide consumed/ (mol of Al.h), are greatly reduced when compared to their (salen)CrX analogues under identical reaction conditions.

  DOI：

  10.1021/ic048508g

文献信息

• Aluminum Salen Complexes and Tetrabutylammonium Salts:  A Binary Catalytic System for Production of Polycarbonates from CO₂ and Cyclohexene Oxide
  作者：Donald J. Darensbourg、Damon R. Billodeaux

  DOI：10.1021/ic048508g

  日期：2005.3.1

  A series of complexes of the form (salen)AIZ, where H(2)salen = N,N'-bis(salicylidene)-1,2-phenylenediimine and various other salen derivatives and Z = Et or Cl, have been synthesized. Several of these complexes have been characterized by X-ray crystallography. An investigation of the utilization of these aluminum derivatives along with both ionic and neutral bases as cocatalysts for the copolymerization of carbon dioxide and cyclohexene oxide has been conducted. By studying the reactivity of these complexes for this process as substituents on the diimine backbone and phenolate rings are altered, we have observed that aluminum prefers electron-withdrawing groups on the salen ligands, thereby producing an electrophilic metal center to be most active toward production of polycarbonates from CO2 and cyclohexene oxide. For example, the complex derived from H(2)salen = N,N'-bis-(3,5-di-tert-butylsalicylidene)-1,2-ethylenediimine is essentially inactive when compared to the analogous derivative containing nitro substituents in the 3-positions of the phenolate groups. This is to be contrasted with the catalytic activity observed for the (salen)CrX systems, where electron-donating salen ligands greatly enhanced the reactivity of these complexes for the coupling Of CO2 and epoxides. While (salen)AIZ complexes are capable of producing poly(cyclohexene oxide) carbonate with low amounts of polyether linkage along with small quantities of cyclic carbonate byproducts, their reactivities, covering a turnover frequency range of 5.2-35.4 mol of epoxide consumed/ (mol of Al.h), are greatly reduced when compared to their (salen)CrX analogues under identical reaction conditions.